Fungicide pyrazole carboxamides derivatives

ABSTRACT

The present invention relates to pyrazole carboxamides derivatives of formula (1) wherein Y represents CR 5  or N, T represents S or O, X1 and X2 represent a chlorine or a fluorine atom, and Z1 represents a substituted or non-substituted cyclopropyl; Their process of preparation, their use as fungicide, and/or anti-mycotoxin active agents, and/or insecticide, and/or nematicide, particularly in the form of fungicide compositions, and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions.

CROSS-REFERENCE TO RELATED APPLICATION(S)

The present application is a divisional of U.S. application Ser. No.13/319,614 filed on Nov. 9, 2011, which is a 35 U.S.C. §371 nationalphase conversion of PCT/EP2010/056521 filed May 12, 2010, which claimspriority of European Application No. 09356035.7 filed May 15, 2009,European Application No. 09356058.9 filed Nov. 19, 2009 and U.S.Provisional Application Ser. No. 61/286,176 filed Dec. 14, 2009.Applicants claim priority to each of the foregoing patent applications.The PCT International Application was published in the English language.

The present invention relates to pyrazole carboxamides derivatives,their process of preparation, their use as fungicide, and/oranti-mycotoxin active agents, and/or insecticide, and/or nematicide,particularly in the form of compositions, and methods for the control ofphytopathogenic fungi, notably of plants, using these compounds orcompositions.

International patent applications WO-2009/016219, WO-2007/087906,WO-2009/016220, WO-2009/016218 and WO-2008/037789 generically mentioncertain amides of the following formulas:

wherein A represents a carbo-linked, partially saturated or unsaturated,5-membered heterocyclyl group that can be substituted, T represents S orN substituted derivatives, Z represents a (un)substituted cycloalkyl.

However, there is no disclosure or suggestion in these documents of anysuch derivative wherein A represent a 1-methyl-3-(difluoro ordichloro)methyl-5-(chloro or fluoro)-4-pyrazolyl.

International patent applications WO-2006/120224 generically mentions2-pyridyl-methylene-carboxamide derivatives of formula:

wherein A represents a carbo-linked 5-membered heterocyclyl group thatcan be substituted and Z³ represents a substituted or non substitutedC₃-C₇ cycloalkyl.

However, there is no disclosure of any derivatives according to theinvention.

In international patent applications WO-2009/016221, certain amides aregenerically embraced in a broad disclosure of numerous compounds of thefollowing formula:

wherein A represents a carbo-linked, unsaturated or partially saturated,5-membered heterocyclyl group that can be substituted and B representsan aromatic 5- or 6-membered, fused heterocyclyl ring comprising up tofour heteroatoms, or an aromatic 6-membered fused carbocyclyl ring.

However there is no disclosure or suggestion in this document of anysuch derivative wherein B is a non fused aryl group.

It is always of high-interest in agriculture to use novel pesticidecompounds in order to avoid or to control the development of resistantstrains to the active ingredients. It is also of high-interest to usenovel compounds being more active than those already known, with the aimof decreasing the amounts of active compound to be used, whilst at thesame time maintaining effectiveness at least equivalent to the alreadyknown compounds. We have now found a new family of compounds thatpossess the above mentioned effects or advantages.

Accordingly, the present invention provides derivatives of formula (I)

wherein

-   -   Y represents CR⁵ or N;    -   T represents S or O;    -   X¹ and X² which can be the same or different, represent a        chlorine or a fluorine atom;    -   Z¹ represents a non substituted cyclopropyl or a cyclopropyl        substituted by up to 2 atoms or groups which can be the same or        different and which can be selected in the list consisting of        halogen atoms; cyano; C₁-C₈-alkyl; or C₁-C₈-halogenoalkyl        comprising up to 9 halogen atoms which can be the same or        different;    -   Z² and Z³, which can be the same or different, represent a        hydrogen atom; substituted or non substituted C₁-C₈-alkyl;        substituted or non substituted C₂-C₈-alkenyl; substituted or non        substituted C₂-C₈-alkynyl; cyano; isonitrile; nitro; a halogen        atom; substituted or non substituted C₁-C₈-alkoxy; substituted        or non substituted C₂-C₈-alkenyloxy; substituted or non        substituted C₂-C₈-alkynyloxy; substituted or non substituted        C₃-C₇-cycloalkyl; substituted or non substituted        C₁-C₈-alkylsulfanyl; substituted or non substituted        C₁-C₈-alkylsulfonyl; substituted or non substituted        C₁-C₈-alkylsulfinyl; amino; substituted or non substituted        C₁-C₈-alkylamino; substituted or non substituted        di-C₁-C₈-alkylamino; substituted or non substituted        C₁-C₈-alkoxycarbonyl; substituted or non substituted        C₁-C₈-alkylcarbamoyl; substituted or non substituted        di-C₁-C₈-alkylcarbamoyl; or substituted or non substituted        N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl; or        -   Z³ and R¹ together with the consecutive carbon atoms to            which they are linked form a substituted or non substituted            5-, 6- or 7-membered, partly saturated, carbo- or            hetero-cycle comprising up to 3 heteroatoms and Z² is as            herein described; or        -   Z² and Z³ together with the carbon atom to which they are            linked form a substituted or non substituted C₃-C₇            cycloalkyl;    -   R¹, R², R³, R⁴ and R⁵, which can be the same or different,        represent a hydrogen atom; a halogen atom; nitro; cyano;        isonitrile; hydroxyl; sulfanyl; amino; pentafluoro-λ⁶-sulfanyl;        substituted or non substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl        comprising up to 9 halogen atoms which can be the same or        different; substituted or non substituted C₁-C₈-alkylamino;        substituted or non substituted di-C₁-C₈-alkylamino; substituted        or non substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy comprising        up to 9 halogen atoms which can be the same or different;        C₁-C₈-alkoxy-C₁-C₈-alkyl; substituted or non substituted        C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl comprising up        to 9 halogen atoms which can be the same or different;        substituted or non substituted C₂-C₈-alkenyl;        C₂-C₈-halogenoalkenyl comprising up to 9 halogen atoms which can        be the same or different; substituted or non substituted        C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl comprising up to 9 halogen        atoms which can be the same or different; substituted or non        substituted C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy        comprising up to 9 halogen atoms which can be the same or        different; substituted or non substituted C₂-C₈-alkynyloxy;        C₂-C₈-halogenoalkynyloxy comprising up to 9 halogen atoms which        can be the same or different; substituted or non substituted        C₃-C₇-cycloalkyl; halogenocycloalkyl comprising up to 9 halogen        atoms which can be the same or different; substituted or non        substituted C₃-C₇-cycloalkyl-C₁-C₈-alkyl; substituted or non        substituted C₃-C₇-cycloalkyl-C₂-C₈-alkenyl; substituted or non        substituted C₃-C₇-cycloalkyl-C₂-C₈-alkynyl; substituted or non        substituted C₃-C₇-cycloalkyl-C₃-C₇-cycloalkyl; substituted or        non substituted C₁-C₈-alkyl-C₃-C₇-cycloalkyl; formyl; formyloxy;        formylamino; carboxy; carbamoyl; N-hydroxycarbamoyl; carbamate;        (hydroxyimino)-C₁-C₈-alkyl; substituted or non substituted        C₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl comprising up        to 9 halogen atoms which can be the same or different;        substituted or non substituted C₁-C₈-alkylcarbamoyl; substituted        or non substituted di-C₁-C₈-alkylcarbamoyl; N-(substituted or        non substituted C₁-C₈-alkyloxy)carbamoyl; substituted or non        substituted C₁-C₈-alkoxycarbamoyl; N-(substituted or non        substituted C₁-C₈-alkyl)-(substituted or non substituted        C₁-C₈-alkoxy)-carbamoyl; substituted or non substituted        C₁-C₈-alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonyl comprising up        to 9 halogen atoms which can be the same or different;        substituted or non substituted C₁-C₈-alkylaminocarbonyl;        di-substituted or non substituted C₁-C₈-alkylaminocarbonyl;        substituted or non substituted C₁-C₈-alkylcarbonyloxy;        C₁-C₈-halogenoalkylcarbonyloxy comprising up to 9 halogen atoms        which can be the same or different; substituted or non        substituted C₁-C₈-alkylcarbonylamino;        C₁-C₈-halogenoalkylcarbonylamino comprising up to 9 halogen        atoms which can be the same or different; substituted or non        substituted C₁-C₈-alkylaminocarbonyloxy; substituted or non        substituted di-C₁-C₈-alkylaminocarbonyloxy; substituted or non        substituted C₁-C₈-alkyloxycarbonyloxy; substituted or non        substituted C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl        comprising up to 9 halogen atoms which can be the same or        different; substituted or non substituted C₁-C₈-alkylsulfonyl;        C₁-C₈-halogenoalkylsulfonyl comprising up to 9 halogen atoms        which can be the same or different; substituted or non        substituted C₁-C₈-alkoxyimino; (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;        substituted or non substituted        (C₁-C₈-alkenyloxyimino)-C₁-C₈-alkyl;        (C₁-C₈-alkynyloxyimino)-C₁-C₈-alkyl; a        (benzyloxyimino)-C₁-C₈-alkyl; tri(substituted or non substituted        C₁-C₈-alkyl)silyl; tri(substituted or non substituted        C₁-C₈-alkyl)silyl-C₁-C₈-alkyl; benzyloxy which can be        substituted by up to 5 groups Q; benzylsulfanyl which can be        substituted by up to 5 groups Q; benzylamino which can be        substituted by up to 5 groups Q; aryl which can be substituted        by up to 7 groups Q; aryloxy which can be substituted by up to 7        groups Q; arylamino which can be substituted by up to 7 groups        Q; arylsulfanyl which can be substituted by up to 7 groups Q;        aryl-C₁-C₈alkyl which can be substituted by up to 7 groups Q;        aryl-C₂-C₈-alkenyl which can be substituted by up to 7 groups Q;        aryl-C₂-C₈-alkynyl which can be substituted by up to 7 groups Q;        pyridinyl which can be substituted by up to 4 groups Q;        pyridinyloxy which can be substituted by up to 4 groups Q;        aryl-C₃-C₇-cycloalkyl which can be substituted by up to 7 groups        Q; or        -   Two vicinal substituents R together with the consecutive            carbon atoms to which they are linked form a substituted or            non substituted 5- or 6-membered, saturated, carbo- or            hetero-cycle comprising up to 3 heteroatoms and the other            substituents R are as herein-described; or    -   R¹ and Z³ together with the consecutive carbon atoms to which        they are linked form a substituted or non substituted 5-, 6- or        7-membered, partly saturated, carbo- or hetero-cycle comprising        up to 3 heteroatoms, and R² to R⁵ are as herein-described;    -   Q, which can be the same or different, represents a halogen        atom; cyano; nitro; C₁-C₈-alkyl; C₁-C₈-alkoxy;        C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkyl comprising up to 9        halogen atoms which can be the same or different;        C₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms which can        be the same or different; tri(C₁-C₈)alkylsilyl or        tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl;        with the provision that when Y represents N, and T represents O,        and Z¹ represents a cyclopropyl group, and R¹ represents a        chlorine atom, and R³ represents a trifluoromethyl group, and R²        and R⁴ represent a hydrogen atom, then a least one of the        substituent Z² or Z³ is not a hydrogen atom,        as well as salts, N-oxydes, metallic complexes, metalloidic        complexes and optically active or geometric isomers thereof.

Unless indicated otherwise, a group or a substituent that is substitutedaccording to the invention can be substituted by one or more of thefollowing groups or atoms: a halogen atom; nitro; hydroxyl; cyano;isonitrile; amino; thio; a pentafluoro-X⁶-sulfanyl group; formyl;formyloxy; formylamino; carbamoyl; N-hydroxycarbamoyl; carbamate;(hydroxyimino)-C₁-C₆-alkyl; C₁-C₈-alkyl; a tri(C₁-C₈-alkyl)silyl;C₃-C₈-cycloalkyl; C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; aC₃-C₈-halogenocycloalkyl having 1 to 5 halogen atoms; C₂-C₈-alkenyl;C₂-C₈-alkynyl; C₂-C₈-alkenyloxy; C₂-C₈-alkynyloxy; C₁-C₈-alkylamino;di-C₁-C₈-alkylamino; C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 5halogen atoms; C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1to 5 halogen atoms; C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy having 1to 5 halogen atoms; C₃-C₈-alkynyloxy; C₃-C₈-halogenoalkynyloxy having 1to 5 halogen atoms; C₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonylhaving 1 to 5 halogen atoms; C₁-C₈-alkylcarbamoyl;di-C₁-C₈-alkylcarbamoyl; N—C₁-C₈-alkyloxycarbamoyl;C₁-C₈-alkoxycarbamoyl; N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl;C₁-C₈-alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogenatoms; C₁-C₈-alkylcarbonyloxy; C₁-C₈-halogenoalkylcarbonyloxy having 1to 5 halogen atoms; C₁-C₈-alkylcarbonylamino;C₁-C₈-halogenoalkylcarbonylamino having 1 to 5 halogen atoms;C₁-C₈-alkylaminocarbonyloxy; di-C₁-C₈-alkylaminocarbonyloxy;C₁-C₈-alkyloxycarbonyloxy; C₁-C₈-alkylsulfanyl;C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogen atoms;C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 5 halogenatoms; C₁-C₈-alkylsulphonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 5halogen atoms; C₁-C₈-alkylaminosulfamoyl; di-C₁-C₈-alkylaminosulfamoyl;(C₁-C₈-alkoxyimino)-C₁-C₆-alkyl; (C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl;(C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl; 2-oxopyrrolidin-1-yl;(benzyloxyimino)-C₁-C₈-alkyl; C₁-C₈-alkoxyalkyl;C₁-C₈-halogenoalkoxyalkyl having 1 to 5 halogen atoms; benzyloxy;benzylsulfanyl; benzylamino; aryloxy; arylsulfanyl or arylamino.

Any of the compounds according to the invention can exist as one or morestereoisomers depending on the number of stereogenic units (as definedby the IUPAC rules) in the compound. The invention thus relates equallyto all the stereoisomers, and to the mixtures of all the possiblestereoisomers, in all proportions. The stereoisomers can be separatedaccording to the methods that are known per se by the man ordinaryskilled in the art.

According to the invention, the following generic terms are generallyused with the following meanings:

-   -   halogen means fluorine, chlorine, bromine or iodine;    -   heteroatom can be nitrogen, oxygen or sulphur;    -   any alkyl, alkenyl or alkynyl group can be linear or branched;    -   the term “aryl” means phenyl or naphthyl, optionally        substituted;    -   In the case of an amino group or the amino moiety of any other        amino-comprising group, substituted by two substituents that can        be the same or different, the two substituents together with the        nitrogen atom to which they are linked can form a heterocyclyl        group, preferably a 5- to 7-membered heterocyclyl group, that        can be substituted or that can include other hetero atoms, for        example a morpholino or piperidinyl group.

Preferred compounds of formula (I) according to the invention are thosewherein Y represents CR⁵.

Other preferred compounds of formula (I) according to the invention arethose wherein Y represents N.

Other preferred compounds of formula (I) according to the invention arethose wherein T represents O.

Other preferred compounds of formula (I) according to the invention arethose wherein X¹ represents a fluorine atom.

Other preferred compounds of formula (I) according to the invention arethose wherein X² represents a fluorine atom.

Other preferred compounds of formula (I) according to the invention arethose wherein Z¹ represents a non substituted cyclopropyl.

Other preferred compounds of formula (I) according to the invention arethose wherein Z² and Z³ independently represent a hydrogen atom or amethyl.

More preferred compounds of formula (I) according to the invention arethose wherein Z² represents a hydrogen atom and Z³ represents a hydrogenatom or a methyl.

Other preferred compounds of formula (I) according to the invention arethose wherein R¹, R², R³, R⁴ and R⁵, which can be the same or different,represent a hydrogen atom; a halogen atom; substituted or nonsubstituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl comprising up to 9 halogenatoms which can be the same or different; substituted or non substitutedC₃-C₇-cycloalkyl; tri(C₁-C₈-alkyl)silyl; or substituted or nonsubstituted C₁-C₈-alkylsulfanyl.

More preferred compounds of formula (I) according to the invention arethose wherein the substituent R¹ represents a halogen atom; C₁-C₈-alkyl;C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms which can be thesame or different; C₃-C₇-cycloalkyl; tri(C₁-C₈-alkyl)silyl orC₁-C₈-halogenoalkylsulfanyl comprising up to 9 halogen atoms which canbe the same or different.

Other more preferred compounds of formula (I) according to the inventionare those wherein the substitutents R¹ and R⁵, which can be the same ordifferent, represent a halogen atom; C₁-C₈-alkyl; C₁-C₈-halogenoalkylcomprising up to 9 halogen atoms which can be the same or different;C₃-C₇-cycloalkyl; tri(C₁-C₈-alkyl)silyl or C₁-C₈-halogenoalkylsulfanylcomprising up to 9 halogen atoms which can be the same or different.

The above mentioned preferences with regard to the substituents of thecompounds of formula (I) according to the invention can be combined invarious manners, either individually, partially or entirely. Thesecombinations of preferred features thus provide sub-classes of compoundsaccording to the invention. Examples of such sub-classes of preferredcompounds according to the invention can combine:

-   -   preferred features of T with preferred features of one or more        X¹, X², Y, Z¹ to Z³, and R¹ to R⁵;    -   preferred features of X¹ with preferred features of one or more        T, X², Y, Z¹ to Z³, and R¹ to R⁵;    -   preferred features of X² with preferred features of one or more        T, X¹, Y, Z¹ to Z³, and R¹ to R⁵;    -   preferred features of Y with preferred features of one or more        T, X¹, X², Z¹ to Z³, and R¹ to R⁵;    -   preferred features of Z¹ with preferred features of one or more        T, X¹, X², Y, Z², Z³, and R¹ to R⁵;    -   preferred features of Z² with preferred features of one or more        T, X¹, X², Y, Z¹, Z³, and R¹ to R⁵;    -   preferred features of Z³ with preferred features of one or more        T, X¹, X², Y, Z₁, Z², and R¹ to R⁵;    -   preferred features of R¹ with preferred features of one or more        T, X¹, X², Y, Z¹ to Z³, and R² to R⁵;    -   preferred features of R² with preferred features of one or more        T, X¹, X², Y, Z¹ to Z³, R¹, and R³ to R⁵;    -   preferred features of R³ with preferred features of one or more        T, X¹, X², Y, Z¹ to Z³, R¹, R², and R⁵;    -   preferred features of R⁴ with preferred features of one or more        T, X¹, X², Y, Z¹ to Z³, R¹ to R³, and R⁵;    -   preferred features of R⁵ with preferred features of one or more        T, X¹, X², Y, Z¹ to Z³, and R¹ to R⁴;

In these combinations of preferred features of the substituents of thecompounds according to the invention, the said preferred features canalso be selected among the more preferred features of each of T, X¹, X²,Y, Z¹ to Z³, and R¹ to R⁵; so as to form most preferred subclasses ofcompounds according to the invention.

The present invention also relates to a process for the preparation ofcompounds of formula (I). Thus according to a further aspect of thepresent invention there is provided a process P1 for the preparation ofcompound of formula (Ia) as herein-defined for which T represents aoxygen atom, as illustrated by the following reaction scheme:

wherein

Z¹, Z², Z³, R¹, R², R³, R⁴, Y and X² are as herein-defined;

5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde is knownfrom WO-2004/014138 (reference example 35).

N-Cyclopropylamines of formula are known (WO-2008/037789,WO-2007/087906, WO-2006/120224 and WO-2009/016218) or can be prepared byknown methods

Step 1 and 13 of process P1 is performed in the presence of an oxidant,and if appropriate in the presence of a solvent.

Steps 2 and 9 of process P1 are performed in the presence of acidhalide, and if appropriate in the presence of a solvent.

Steps 4, 7 and 10 of process P1 are performed in the presence of an acidbinder, and if appropriate in the presence of a solvent.

Steps 3 and 8 of process P1 are performed in the presence of acondensing agent, and if appropriate in the presence of a solvent.

Step 5 and 12 of process P1 is performed in the presence of afluorinating agent, and if appropriate in the presence of a solvent.

Step 11 of process P1 is performed in the presence of a chlorinatingagent and a lewis acid, and if appropriate in the presence of a solvent.

According to a further aspect of the present invention there is provideda process P2 for the preparation of compound of formula (Ia) asherein-defined for which T represent a oxygen atom, as illustrated bythe following reaction scheme:

wherein

Z¹, Z², Z³, Y, R¹, R², R³, R⁴, X¹ and X² are as herein-defined;

W¹ represents a halogen atom or a hydroxyl;

W² represents a halogen or a leaving group such as tosylate, mesylate ortriflate group.

Pyrazoles derivatives of formula (IIh) may be prepared according toprocess P1.

N-cyclopropylamines of formula (IV) and methylene derivatives of formula(V) are known or may be prepared by known methods.

Step 1 of process P2 is performed in the presence of an acid binder or acondensing agent, and if appropriate in the presence of a solvent.

Step 2 of process P2 is performed in the presence of a solvent and ifappropriate in the presence of an acid binder.

According to a further aspect of the present invention there is provideda process P3 for the preparation of compound of formula (Ib) asherein-defined for which T represent a sulfur atom, as illustrated bythe following reaction scheme:

wherein

Z¹, Z², Z³, Y, R¹, R², R³, R⁴, X¹ and X² are as herein-defined;

Step 1 of process P3 is performed in the presence of a thionating agentand if appropriate in the presence of an acid binder and if appropriatein the presence of solvent.

Suitable oxidants for carrying out step 1 or 13 of process P1 accordingto the invention are in each case all inorganic and organic oxidantwhich are customary for such reactions. Preference is given to usingbenzyltriethylammonium permanganate; bromine; chlorine;m-chloroperbenzoic acid; chromic acid; chromium (VI) oxide; hydrogenperoxide; hydrogen peroxide-boron trifluoride; hydrogen peroxide-urea;2-hydroxyperoxyhexafluoro-2-propanol; Iodine; oxygen-platinum catalyst,perbenzoic acid; peroxyacetyl nitrate; potassium permanganate; potassiumruthenate; pyridinium dichromate; ruthenium (VIII) oxide; silver (I)oxide; silver (II) oxide; silver nitrite; sodium chlorite; sodiumhypochlorite; 2,2,6,6-tetramethylpiperidin-1-oxyl.

Suitable acid halides for carrying out steps 2 and 9 of process P1according to the invention are in each case all organic or inorganicacid halides which are customary for such reactions. Preference is givento using notably phosgene, phosphorous trichloride, phosphorouspentachloride, phosphorous trichloride oxide; thionyl chloride; orcarbon tetrachloride-triphenylphosphine.

Suitable acid binder for carrying out steps 4, 7 and 10 of process P1,steps 1 and 2 of process P2 and process P3 according to the inventionare in each case all inorganic and organic bases which are customary forsuch reactions. Preference is given to using alkaline earth metal,alkali metal hydride, alkali metal hydroxides or alkali metal alkoxydes,such as sodium hydroxide, sodium hydride, calcium hydroxide, potassiumhydroxide, potassium tert-butoxide or other ammonium hydroxide, alkalimetal carbonates, such as sodium carbonate, potassium carbonate,potassium bicarbonate, sodium bicarbonate, alkali metal or alkalineearth metal acetates, such as sodium acetate, potassium acetate, calciumacetate, and also ternary amines, such as trimethylamine, triethylamine,tributylamine, N,N-dimethylaniline, di-isopropyl-ethylamine, pyridine,methylethylpyridine, methylimidazole, N-methylpiperidine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU).

It is also possible to work in the absence of an acid binder or toemploy an excess of the amine component, so that it simultaneously actsas acid binder agent.

Suitable condensing agent for carrying out steps 3 and 8 of process P1and step 1 of process P2 according to the invention are in each case allcondensing agents which are customary for such reactions. Preference isgiven to using carbodiimides, such as N,N′-dicyclohexylcarbodiimide(DCC) or other customary condensing agents, notably phosphorouspentoxide, polyphosphoric acid, N,N′-carbonyldiimidazole,2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ),triphenylphosphine/tetrachloromethane orbromo-tripyrrolidinophosphonium-hexafluorophosphate.

Suitable fluorinating agent for carrying out step 5 or 12 of process P1according to the invention is in each case all fluorinating agents whichare customary for such reactions. Preference is given to using cesiumfluoride; potassium fluoride; potassium fluoride-calcium difluoride;tetrabutylammonium fluoride.

Suitable chlorination agent for carrying out step 11 of process P1according to the invention is in each case all chlorination agentsagents which are customary for such reactions (WO-2007/062776).Preference is given to using tetrachlorosilane/aluminium trichloride,aluminium trichloride.

Suitable thionating agents for carrying out process P3 according to theinvention can be sulphur (S), sulfhydric acid (H2S), sodium sulfide(Na₂S), sodium hydrosulfide (NaHS), boron trisulfide (B₂S₃),bis(diethylaluminium) sulfide ((AlEt₂)₂S), ammonium sulfide ((NH₄)₂S),phosphorous pentasulfide (P₂S₅), Lawesson's reagent(2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide) ora polymer-supported thionating reagent such as described in J. Chem.Soc. Perkin 1, (2001), 358.

Suitable solvents for carrying out steps 1 to 13 of process P1, steps 1and 2 of process P2 and process P3 according to the invention are ineach case all customary inert organic solvents. Preference is given tousing optionally halogenated aliphatic, alicyclic or aromatichydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene,dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride,dichlorethane or trichlorethane; ethers, such as diethyl ether,cyclopentyl methylether, diisopropyl ether, methyl t-butyl ether, methylt-amyl ether, dioxane, tetrahydrofuran, 2-methyl tetrahydrofuran,1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitriles, such asacetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile;amides, such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methylformanilide, N-methylpyrrolidone or hexamethylphosphorictriamide; esters, such as methyl acetate or ethyl acetate, sulphoxides,such as dimethyl sulphoxide, or sulphones, such as sulpholane.

When carrying out steps 1 to 13 of process P1 and steps 1 and 2 ofprocess P2 according to the invention, the reaction temperatures canindependently be varied within a relatively wide range. Generally,processes according to the invention are carried out at temperaturesbetween 0° C. and 160° C., preferably between 10° C. and 120° C. A wayto control the temperature for the processes according to the inventionis to use the micro-waves technology.

Steps 1 to 13 of process P1 and steps 1 and 2 of process P2 according tothe invention are generally independently carried out under atmosphericpressure. However, in each case, it is also possible to operate underelevated or reduced pressure.

When carrying out step 1 or 13 of process P1 according to the invention,generally 1 mol or other an excess of the oxidant is employed per moleof aldehyde of formula (IIa) or (IIg). It is also possible to employ thereaction components in other ratios.

When carrying out carrying out steps 2 and 9 of process P1 to theinvention, generally 1 mol or other an excess of the acid halides isemployed per mole of acid of formula (IIb) or (IIe). It is also possibleto employ the reaction components in other ratios.

When carrying out steps 4, 7 and 10 of process P1 and step 1 and 2 ofprocess P2 according to the invention generally 1 mol or other an excessof the acid binder is employed per mole of acid halides of formula(IIc), (IId) or (IIf). It is also possible to employ the reactioncomponents in other ratios.

When carrying out process P3 according to the invention, generally 1 molor other an excess of the acid binder is employed per mole of compound(Ia). It is also possible to employ the reaction components in otherratios.

When carrying out steps 3 and 8 of process P1 and step 1 of process P2according to the invention generally 1 mol or other an excess of thecondensing agent is employed per mole of acid of formula (IIb) and(IIe). It is also possible to employ the reaction components in otherratios.

When carrying out step 5 or 12 of process P1 according to the invention,generally 2 moles or other an excess of the fluorinating agent isemployed per mole of chlorinated compound of formula (IIa) or (IIc). Itis also possible to employ the reaction components in other ratios.

When carrying out step 11 of process P1 according to the invention,generally 0.2-0.3 mol of chlorinating agent is employed per mole of acidfluoride formula (IId). It is also possible to employ the reactioncomponents in other ratios.

Work-up is carried out by customary methods. Generally, the reactionmixture is treated with water and the organic phase is separated offand, after drying, concentrated under reduced pressure. If appropriate,the remaining residue can, be freed by customary methods, such aschromatography, recrystallization or distillation, from any impuritiesthat may still be present.

Compounds according to the invention can be prepared according to theabove described process. It will nevertheless be understood that, on thebasis of his general knowledge and of available publications, theskilled worker will be able to adapt these processes according to thespecifics of each of the compounds according to the invention that isdesired to be synthesized.

Still in a further aspect, the present invention relates to compounds offormula (II) useful as intermediate compounds or materials for theprocess of preparation according to the invention.

The present invention thus provides:

-   -   compounds of formula (IIb)

wherein X² represents a chlorine or a fluorine atom, preferably afluorine atom;

-   -   compounds of formula (IIc′)

wherein X² represents a chlorine or a fluorine atom, preferably afluorine atom and W³ represent a halogen atom preferably a chlorineatom;

-   -   compounds of formula (IId)

wherein X² represents a chlorine or a fluorine atom, preferably afluorine atom;

-   -   compounds of formula (IIe)

wherein X² represents a chlorine or a fluorine atom, preferably afluorine atom.

-   -   compounds of formula (IIf)

wherein X² represents a chlorine or a fluorine atom, preferably afluorine atom.

-   -   compounds of formula (IIg)

wherein X² represents a chlorine or a fluorine atom, preferably afluorine atom.

In a further aspect, the present invention also relates to acomposition, particularly a fungicide composition, comprising aneffective and non-phytotoxic amount of an active compound of formula(I).

The expression “effective and non-phytotoxic amount” means an amount ofcomposition according to the invention that is sufficient to control ordestroy the fungi, and/or insects, and/or nematicides, and/or weedspresent or liable to appear on or around the crops, and that does notentail any appreciable symptom of phytotoxicity for the said crops. Suchan amount can vary within a wide range depending on the target,particularly fungus, to be controlled, the type of crop, the climaticconditions and the compounds included in the composition according tothe invention. This amount can be determined by systematic field trials,that are within the capabilities of a person skilled in the art.

Thus, according to the invention, there is provided a composition,particularly a fungicide composition, comprising, as an activeingredient, an effective amount of a compound of formula (I) as hereindefined and an agriculturally acceptable support, carrier or filler.

According to the invention, the term “support” denotes a natural orsynthetic, organic or inorganic compound with that the active compoundof formula (I) is combined or associated to make it easier to apply,notably to the parts of the plant. This support is thus generally inertand should be agriculturally acceptable. The support can be a solid or aliquid. Examples of suitable supports include clays, natural orsynthetic silicates, silica, resins, waxes, solid fertilisers, water,alcohols, in particular butanol, organic solvents, mineral and plantoils and derivatives thereof. Mixtures of such supports can also beused.

The composition according to the invention can also comprise additionalcomponents. In particular, the composition can further comprise asurfactant. The surfactant can be an emulsifier, a dispersing agent or awetting agent of ionic or non-ionic type or a mixture of suchsurfactants. Mention can be made, for example, of polyacrylic acidsalts, lignosulphonic acid salts, phenolsulphonic ornaphthalenesulphonic acid salts, polycondensates of ethylene oxide withfatty alcohols or with fatty acids or with fatty amines, substitutedphenols (in particular alkylphenols or arylphenols), salts ofsulphosuccinic acid esters, taurine derivatives (in particular alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols,fatty acid esters of polyols, and derivatives of the above compoundscomprising sulphate, sulphonate and phosphate functions. The presence ofat least one surfactant is generally essential when the active compoundand/or the inert support are water-insoluble and when the vector agentfor the application is water. Preferably, surfactant content can becomprised from 5% to 40% by weight of the composition.

Optionally, additional components can also be included, e.g. protectivecolloids, adhesives, thickeners, thixotropic agents, penetration agents,stabilisers, sequestering agents. More generally, the active compoundscan be combined with any solid or liquid additive, that complies withthe usual formulation techniques.

In general, the composition according to the invention can contain from0.05 to 99% by weight of active compound, preferably 10 to 70% byweight.

Compositions according to the invention can be used in various formssuch as aerosol dispenser, capsule suspension, cold fogging concentrate,dustable powder, emulsifiable concentrate, emulsion oil in water,emulsion water in oil, encapsulated granule, fine granule, to flowableconcentrate for seed treatment, gas (under pressure), gas generatingproduct, granule, hot fogging concentrate, macrogranule, microgranule,oil dispersible powder, oil miscible flowable concentrate, oil miscibleliquid, paste, plant rodlet, powder for dry seed treatment, seed coatedwith a pesticide, soluble concentrate, soluble powder, solution for seedtreatment, suspension concentrate (flowable concentrate), ultra lowvolume (ULV) liquid, ultra low volume (ULV) suspension, waterdispersible granules or tablets, water dispersible powder for slurrytreatment, water soluble granules or tablets, water soluble powder forseed treatment and wettable powder. These compositions include not onlycompositions that are ready to be applied to the plant or seed to betreated by means of a suitable device, such as a spraying or dustingdevice, but also concentrated commercial compositions that must bediluted before application to the crop.

The compounds according to the invention can also be mixed with one ormore insecticide, fungicide, bactericide, attractant, acaricide orpheromone active substance or other compounds with biological activity.The mixtures thus obtained have normally a broadened spectrum ofactivity. The mixtures with other fungicide compounds are particularlyadvantageous.

Examples of suitable fungicide mixing partners can be selected in thefollowing lists:

-   (1) Inhibitors of the ergosterol biosynthesis, for example (1.1)    aldimorph (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3)    bitertanol (55179-31-2), (1.4) bromuconazole (116255-48-2), (1.5)    cyproconazole (113096-99-4), (1.6) diclobutrazole (75736-33-3),    (1.7) difenoconazole (119446-68-3), (1.8) diniconazole (83657-24-3),    (1.9) diniconazole-M (83657-18-5), (1.10) dodemorph (1593-77-7),    (1.11) dodemorph acetate (31717-87-0), (1.12) epoxiconazole    (106325-08-0), (1.13) etaconazole (60207-93-4), (1.14) fenarimol    (60168-88-9), (1.15) fenbuconazole (114369-43-6), (1.16) fenhexamid    (126833-17-8), (1.17) fenpropidin (67306-00-7), (1.18) fenpropimorph    (67306-03-0), (1.19) fluquinconazole (136426-54-5), (1.20)    flurprimidol (56425-91-3), (1.21) flusilazole (85509-19-9), (1.22)    flutriafol (76674-21-0), (1.23) furconazole (112839-33-5), (1.24)    furconazole-cis (112839-32-4), (1.25) hexaconazole (79983-71-4),    (1.26) imazalil (60534-80-7), (1.27) imazalil sulfate (58594-72-2),    (1.28) imibenconazole (86598-92-7), (1.29) ipconazole (125225-28-7),    (1.30) metconazole (125116-23-6), (1.31) myclobutanil (88671-89-0),    (1.32) naftifine (65472-88-0), (1.33) nuarimol (63284-71-9), (1.34)    oxpoconazole (174212-12-5), (1.35) paclobutrazol (76738-62-0),    (1.36) pefurazoate (101903-30-4), (1.37) penconazole (66246-88-6),    (1.38) piperalin (3478-94-2), (1.39) prochloraz (67747-09-5), (1.40)    propiconazole (60207-90-1), (1.41) prothioconazole (178928-70-6),    (1.42) pyributicarb (88678-67-5), (1.43) pyrifenox (88283-41-4),    (1.44) quinconazole (103970-75-8), (1.45) simeconazole    (149508-90-7), (1.46) spiroxamine (118134-30-8), (1.47) tebuconazole    (107534-96-3), (1.48) terbinafine (91161-71-6), (1.49) tetraconazole    (112281-77-3), (1.50) triadimefon (43121-43-3), (1.51) triadimenol    (89482-17-7), (1.52) tridemorph (81412-43-3), (1.53) triflumizole    (68694-11-1), (1.54) triforine (26644-46-2), (1.55) triticonazole    (131983-72-7), (1.56) uniconazole (83657-22-1), (1.57) uniconazole-p    (83657-17-4), (1.58) viniconazole (77174-66-4), (1.59) voriconazole    (137234-62-9), (1.60)    1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol    (129586-32-9), (1.61) methyl    1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazole-5-carboxylate    (111323-95-0), (1.62)    N′-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide,    (1.63)    N-ethyl-N-methyl-N′-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamide    and (1.64) O-[1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl]    1H-imidazole-1-carbothioate (111226-71-2).-   (2) inhibitors of the respiratory chain at complex I or II, for    example (2.1) bixafen (581809-46-03), (2.2) boscalid (188425-85-6),    (2.3) carboxin (5234-68-4), (2.4) diflumetorim (130339-07-0), (2.5)    fenfuram (24691-80-3), (2.6) fluopyram (658066-35-4), (2.7)    flutolanil (66332-96-5), (2.8) furametpyr (123572-88-3), (2.9)    furmecyclox (60568-05-0), (2.10) isopyrazam (mixture of syn-epimeric    racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR)    (881685-58-1), (2.11) isopyrazam (anti-epimeric racemate    1RS,4SR,9SR), (2.12) isopyrazam (anti-epimeric enantiomer 1R,4S,9S),    (2.13) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.14)    isopyrazam (syn epimeric racemate 1RS,4SR,9RS), (2.15) isopyrazam    (syn-epimeric enantiomer 1R,4S,9R), (2.16) isopyrazam (syn-epimeric    enantiomer 1S,4R,9S), (2.17) mepronil (55814-41-0), (2.18)    oxycarboxin (5259-88-1), (2.19) penflufen (494793-67-8), (2.20)    penthiopyrad (183675-82-3), (2.21) sedaxane (874967-67-6), (2.22)    thifluzamide (130000-40-7), (2.23)    1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide,    (2.24) fluxapyroxad (907204-31-3), (2.25)    3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide,    (2.26) 3-(d    ifluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide,    (2.27)    N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,    and salts thereof.-   (3) inhibitors of the respiratory chain at complex III, for example    (3.1) amisulbrom (348635-87-0), (3.2) azoxystrobin (131860-33-8),    (3.3) cyazofamid (120116-88-3), (3.4) dimoxystrobin (141600-52-4),    (3.5) enestroburin (238410-11-2) (known from WO 2004/058723), (3.6)    famoxadone (131807-57-3) (known from WO 2004/058723), (3.7)    fenamidone (161326-34-7) (known from WO 2004/058723), (3.8)    fluoxastrobin (361377-29-9) (known from WO 2004/058723), (3.9)    kresoxim-methyl (143390-89-0) (known from WO 2004/058723), (3.10)    metominostrobin (133408-50-1) (known from WO 2004/058723), (3.11)    orysastrobin (189892-69-1) (known from WO 2004/058723), (3.12)    picoxystrobin (117428-22-5) (known from WO 2004/058723), (3.13)    pyraclostrobin (175013-18-0) (known from WO 2004/058723), (3.14)    pyrametostrobin (915410-70-7) (known from WO 2004/058723), (3.15)    pyraoxystrobin (862588-11-2) (known from WO 2004/058723), (3.16)    pyribencarb (799247-52-2) (known from WO 2004/058723), (3.17)    trifloxystrobin (141517-21-7) (known from WO 2004/058723), (3.18)    (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide    (known from WO 2004/058723), (3.19)    (2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanamide    (known from WO 2004/058723) and salts thereof, (3.20)    (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3-(trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamide    (158169-73-4), (3.21)    (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide    (326896-28-0), (3.22)    (2E)-2-{2-[({[(2E,3E)-4-(2,6-dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide,    (3.23)    2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)pyridine-3-carboxamide    (119899-14-8), (3.24)    5-methoxy-2-methyl-4-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one,    (3.25) methyl    (2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}sulfanyl)methyl]phenyl}-3-methoxyprop-2-enoate    (149601-03-6), (3.26)    N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide    (226551-21-9), (3.27)    2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide    (173662-97-0), (3.28)    (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide    (394657-24-0) and salts thereof.-   (4) Inhibitors of the mitosis and cell division, for example (4.1)    benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3)    chlorfenazole (3574-96-7), (4.4) diethofencarb (87130-20-9), (4.5)    ethaboxam (162650-77-3), (4.6) fluopicolide (239110-15-7), (4.7)    fuberidazole (3878-19-1), (4.8) pencycuron (66063-05-6), (4.9)    thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8),    (4.11) thiophanate (23564-06-9), (4.12) zoxamide (156052-68-5),    (4.13)    5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine    (214706-53-3) and (4.14)    3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine    (1002756-87-7) and salts thereof.-   (5) Compounds capable to have a multisite action, like for example    (5.1) bordeaux mixture (8011-63-0), (5.2) captafol (2425-06-1),    (5.3) captan (133-06-2) (known from WO 02/12172), (5.4)    chlorothalonil (1897-45-6), (5.5) copper hydroxide (20427-59-2),    (5.6) copper naphthenate (1338-02-9), (5.7) copper oxide    (1317-39-1), (5.8) copper oxychloride (1332-40-7), (5.9) copper(2+)    sulfate (7758-98-7), (5.10) dichlofluanid (1085-98-9), (5.11)    dithianon (3347-22-6), (5.12) dodine (2439-10-3), (5.13) dodine free    base, (5.14) ferbam (14484-64-1), (5.15) fluorofolpet (719-96-0),    (5.16) folpet (133-07-3), (5.17) guazatine (108173-90-6), (5.18)    guazatine acetate, (5.19) iminoctadine (13516-27-3), (5.20)    iminoctadine albesilate (169202-06-6), (5.21) iminoctadine    triacetate (57520-17-9), (5.22) mancopper (53988-93-5), (5.23) to    mancozeb (2234562), (5.24) maneb (12427-38-2), (5.25) metiram    (9006-42-2), (5.26) metiram zinc (9006-42-2), (5.27) oxine-copper    (10380-28-6), (5.28) propamidine (104-32-5), (5.29) propineb    (12071-83-9), (5.30) sulphur and sulphur preparations including    calcium polysulphide (7704-34-9), (5.31) thiram (137-26-8), (5.32)    tolylfluanid (731-27-1), (5.33) zineb (12122-67-7), (5.34) ziram    (137-30-4) and salts thereof.-   (6) Compounds capable to induce a host defence, like for example    (6.1) acibenzolar-5-methyl (135158-54-2), (6.2) isotianil    (224049-04-1), (6.3) probenazole (27605-76-1) and (6.4) tiadinil    (223580-51-6).-   (7) Inhibitors of the amino acid and/or protein biosynthesis, for    example (7.1) andoprim (23951-85-1), (7.2) blasticidin-S    (2079-00-7), (7.3) cyprodinil (121552-61-2), (7.4) kasugamycin    (6980-18-3), (7.5) kasugamycin hydrochloride hydrate (19408-46-9),    (7.6) mepanipyrim (110235-47-7) and (7.7) pyrimethanil (53112-28-0).-   (8) Inhibitors of the ATP production, for example (8.1) fentin    acetate (900-95-8), (8.2) fentin chloride (639-58-7), (8.3) fentin    hydroxide (76-87-9) and (8.4) silthiofam (175217-20-6).-   (9) Inhibitors of the cell wall synthesis, for example (9.1)    benthiavalicarb (177406-68-7), (9.2) dimethomorph (110488-70-5),    (9.3) flumorph (211867-47-9), (9.4) iprovalicarb (140923-17-7),    (9.5) mandipropamid (374726-62-2), (9.6) polyoxins (11113-80-7),    (9.7) polyoxorim (22976-86-9), (9.8) validamycin A (37248-47-8) and    (9.9) valifenalate (283159-94-4; 283159-90-0).-   (10) Inhibitors of the lipid and membrane synthesis, for example    (10.1) biphenyl (92-52-4), (10.2) chloroneb (2675-77-6), (10.3)    dicloran (99-30-9), (10.4) edifenphos (17109-49-8), (10.5)    etridiazole (2593-15-9), (10.6) iodocarb (55406-53-6), (10.7)    iprobenfos (26087-47-8), (10.8) isoprothiolane (50512-35-1), (10.9)    propamocarb (25606-41-1), (10.10) propamocarb hydrochloride    (25606-41-1), (10.11) prothiocarb (19622-08-3), (10.12) pyrazophos    (13457-18-6), (10.13) quintozene (82-68-8), (10.14) tecnazene    (117-18-0) and (10.15) tolclofos-methyl (57018-04-9).-   (11) Inhibitors of the melanine biosynthesis, for example (11.1)    carpropamid (104030-54-8), (11.2) diclocymet (139920-32-4), (11.3)    fenoxanil (115852-48-7), (11.4) phthalide (27355-22-2), (11.5)    pyroquilon (57369-32-1) and (11.6) tricyclazole (41814-78-2).-   (12) Inhibitors of the nucleic acid synthesis, for example (12.1)    benalaxyl (71626-11-4), (12.2) benalaxyl-M (kiralaxyl) (98243-83-5),    (12.3) bupirimate (41483-43-6), (12.4) clozylacon (67932-85-8),    (12.5) dimethirimol (5221-53-4), (12.6) ethirimol (23947-60-6),    (12.7) furalaxyl (57646-30-7), (12.8) hymexazol (10004-44-1), (12.9)    metalaxyl (57837-19-1), (12.10) metalaxyl-M (mefenoxam)    (70630-17-0), (12.11) ofurace (58810-48-3), (12.12) oxadixyl    (77732-09-3) and (12.13) oxolinic acid (14698-29-4).-   (13) Inhibitors of the signal transduction, for example (13.1)    chlozolinate (84332-86-5), (13.2) fenpiclonil (74738-17-3), (13.3)    fludioxonil (131341-86-1), (13.4) iprodione (36734-19-7), (13.5)    procymidone (32809-16-8), (13.6) quinoxyfen (124495-18-7) and (13.7)    vinclozolin (50471-44-8).-   (14) Compounds capable to act as an uncoupler, like for example    (14.1) binapacryl (485-31-4), (14.2) dinocap (131-72-6), (14.3)    ferimzone (89269-64-7), (14.4) fluazinam (79622-59-6) and (14.5)    meptyldinocap (131-72-6).-   (15) Further compounds like for example (15.1)    1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone,    (15.2) 1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl    1H-imidazole-1-carboxylate (111227-17-9), (15.3)    2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (13108-52-6), (15.4)    2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one (221451-58-7),    (15.5)    2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5R)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone,    (15.6) 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, (15.7)    2-phenylphenol and salts (90-43-7), (15.8)    3,4,5-trichloropyridine-2,6-dicarbonitrile (17824-85-0), (15.9)    3-[5-(4-chlorophenyl)-2,3-dimethyl-1,2-oxazolidin-3-yl]pyridine,    (15.10)    3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine,    (15.11)    4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine,    (15.12) 5-amino-1,3,4-thiadiazole-2-thiol, (15.13)    5-chloro-N′-phenyl-N′-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide    (134-31-6), (15.14)    5-methyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidin-7-amine, (15.15)    ametoctradin (865318-97-4), (15.16) benthiazole (21564-17-0),    (15.17) bethoxazin (163269-30-5), (15.18) capsimycin (70694-08-5),    (15.19) carvone (99-49-0), (15.20) chinomethionat (2439-01-2),    (15.21) chlazafenone (688046-61-9), (15.22) cufraneb (11096-18-7),    (15.23) cyflufenamid (180409-60-3), (15.24) cymoxanil (57966-95-7),    (15.25) cyprosulfamide (221667-31-8), (15.26) dazomet (533-74-4),    (15.27) debacarb (62732-91-6), (15.28) dichlorophen (97-23-4),    (15.29) diclomezine (62865-36-5), (15.30) difenzoquat (43222-48-6),    (15.31) difenzoquat methylsulphate (43222-48-6), (15.32)    diphenylamine (122-39-4), (15.33) ecomate, (15.34) ethyl    (2Z)-3-amino-2-cyano-3-phenylprop-2-enoate, (15.35) flumetover    (154025-04-4), (15.36) fluoroimide (41205-21-4), (15.37)    flusulfamide (106917-52-6), (15.38) flutianil (304900-25-2), (15.39)    fosetyl-aluminium (39148-24-8), (15.40) fosetyl-calcium, (15.41)    fosetyl-sodium (39148-16-8), (15.42) hexachlorobenzene (118-74-1),    (15.43) irumamycin (81604-73-1), (15.44) methasulfocarb    (66952-49-6), (15.45) methyl isothiocyanate (556-61-6), (15.46)    metrafenone (220899-03-6), (15.47) mildiomycin (67527-71-3), (15.48)    N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide,    (15.49)    N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide,    (15.50)    N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3-carboxamide,    (15.51)    N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide,    (15.52)    N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine-3-carboxamide,    (15.53)    N-{(E)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide,    (15.54)    N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide    (221201-92-9), (15.55) natamycin (7681-93-8), (15.56) nickel    dimethyldithiocarbamate (15521-65-0), (15.57) nitrothal-isopropyl    (10552-74-6), (15.58)    N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-(1,2,3,4-tetrahydronaphthalen-1-yl)-1,3-thiazole-4-carboxamide,    (15.59)    N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide,    (15.60) octhilinone (26530-20-1), (15.61) oxamocarb (917242-12-7),    (15.62) oxyfenthiin (34407-87-9), (15.63) pentachlorophenol and    salts (87-86-5), (15.64) pentyl    {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylidene]amino}oxy)methyl]pyridin-2-yl}carbamate,    (15.65) phenazine-1-carboxylic acid, (15.66) phenothrin, (15.67)    phosphorous acid and its salts (13598-36-2), (15.68)    propamocarb-fosetylate, (15.69) propanosine-sodium (88498-02-6),    (15.70) proquinazid (189278-12-4), (15.71) pyrroInitrine (1018-71-9)    (known from EP-A 1 559 320), (15.72) quinolin-8-ol (134-31-6),    (15.73) quinolin-8-ol sulfate (2:1) (134-31-6), (15.74)    fenpyrazamine (473798-59-3), (15.75) tebufloquin (376645-78-2),    (15.76) tecloftalam (76280-91-6), (15.77) tolnifanide (304911-98-6),    (15.78) triazoxide (72459-58-6), (15.79) trichlamide (70193-21-4),    (15.80) zarilamid (84527-51-5) and salts thereof.-   (16) Further compounds like for example (2.27)    1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide,    (2.28)    N-(4′-chlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,    (2.29)    N-(2′,4′-dichlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,    (2.30)    3-(difluoromethyl)-1-methyl-N-[4′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide,    (2.31)    N-(2′,5′-difluorobiphenyl-2-yl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide,    (2.32)    3-(difluoromethyl)-1-methyl-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide    (known from WO 2004/058723), (2.33)    5-fluoro-1,3-dimethyl-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide    (known from WO 2004/058723), (2.34)    2-chloro-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide    (known from WO 2004/058723), (2.35)    3-(difluoromethyl)-N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide    (known from WO 2004/058723), (2.36)    N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide    (known from WO 2004/058723), (2.37)    3-(difluoromethyl)-N-(4′-ethynylbiphenyl-2-yl)-1-methyl-1H-pyrazole-4-carboxamide    (known from WO 2004/058723), (2.38)    N-(4′-ethynylbiphenyl-2-yl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide    (known from WO 2004/058723), (2.39)    2-chloro-N-(4′-ethynylbiphenyl-2-yl)pyridine-3-carboxamide (known    from WO 2004/058723), (2.40)    2-chloro-N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide    (known from WO 2004/058723), (2.41)    4-(difluoromethyl)-2-methyl-N-[4′-(trifluoromethyl)biphenyl-2-yl]-1,3-thiazole-5-carboxamide    (known from WO 2004/058723), (2.42)    5-fluoro-N-[4′-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide    (known from WO 2004/058723), (2.43)    2-chloro-N-[4′-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide    (known from WO 2004/058723), (2.44)    3-(difluoromethyl)-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide    (known from WO 2004/058723), (2.45)    5-fluoro-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide    (known from WO 2004/058723), (2.46)    2-chloro-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide    (known from WO 2004/058723) and salts thereof, (15.81)    (5-bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanone    (known from EP-A 1 559 320) and (9.10)    N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl]-N-2-(methylsulfonyl)valinamide    (220706-93-4).

The composition according to the invention comprising a mixture of acompound of formula (I) with a bactericide compound can also beparticularly advantageous. Examples of suitable bactericide mixingpartners can be selected in the following list: bronopol, dichlorophen,nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone,furancarboxylic acid, oxytetracycline, probenazole, streptomycin,tecloftalam, copper sulphate and other copper preparations.

The compounds of formula (I) and the fungicide composition according tothe invention can be used to curatively or preventively control thephytopathogenic fungi of plants or crops.

Thus, according to a further aspect of the invention, there is provideda method for curatively or preventively controlling the phytopathogenicfungi of plants or crops characterised in that a compound of formula (I)or a fungicide composition according to the invention is applied to theseed, the plant or to the fruit of the plant or to the soil wherein theplant is growing or wherein it is desired to grow.

The method of treatment according to the invention can also be useful totreat propagation material such as tubers or rhizomes, but also seeds,seedlings or seedlings pricking out and plants or plants pricking out.This method of treatment can also be useful to treat roots. The methodof treatment according to the invention can also be useful to treat theoverground parts of the plant such as trunks, stems or stalks, leaves,flowers and fruit of the concerned plant.

Among the plants that may be protected by the method according to theinvention, mention may be made of cotton; flax; vine; fruit or vegetablecrops such as Rosaceae sp. (for instance pip fruit such as apples andpears, but also stone fruit such as apricots, almonds and peaches),Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp.,Fagaceae sp., Moraceae sp., Oleaceae sp., Actimidaceae sp., Lauraceaesp., Musaceae sp. (for instance banana trees and plantins), Rubiaceaesp., Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemonsoranges and grapefruit); Solanaceae sp. (for instance tomatoes),Liliaceae sp., Asteraceae sp. (for instance lettuces), Umbelliferae sp.,Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp.(for instance peas), Rosaceae sp. (for instance strawberries); majorcrops such as Graminae sp. (for instance maize, lawn or cereals such aswheat, rye, rice, barley and triticale), Asteraceae sp. (for instancesunflower), Cruciferae sp. (for instance colza), Fabacae sp. (forinstance peanuts), Papilionaceae sp. (for instance soybean), Solanaceaesp. (for instance potatoes), Chenopodiaceae sp. (for instancebeetroots), Elaeis sp. (for instance oil palm); horticultural and forestcrops; as well as genetically modified homologues of these crops.

Among the diseases of plants or crops that can be controlled by themethod according to the invention, mention can be made of:

-   -   Powdery Mildew Diseases such as    -   Blumeria diseases caused for example by Blumeria graminis;    -   Podosphaera diseases caused for example by Podosphaera        leucotricha;    -   Sphaerotheca diseases caused for example by Sphaerotheca        fuliginea;    -   Uncinula diseases caused for example by Uncinula necator;    -   Rust Diseases such as    -   Gymnosporangium diseases caused for example by Gymnosporangium        sabinae;    -   Hemileia diseases caused for example by Hemileia vastatrix;    -   Phakopsora diseases caused for example by Phakopsora pachyrhizi        and Phakopsora meibomiae;    -   Puccinia diseases caused for example by Puccinia recondita,        Puccinia graminis or Puccinia striiformis;    -   Uromyces diseases caused for example by Uromyces appendiculatus;    -   Oomycete Diseases such as    -   Albugo diseases caused for example by Albugo candida;    -   Bremia diseases caused for example by Bremia lactucea;    -   Peronospora diseases caused for example by Peronospora pisi and        Peronospora brassicae;    -   Phytophthora diseases caused for example by Phytophthora        infestans;    -   Plasmopara diseases caused for example by Plasmopara viticola;    -   Pseudoperonospora diseases caused for example by        Pseudoperonospora humuli and Pseudoperonospora cubensis;    -   Pythium diseases caused for example by Pythium ultimum;    -   Leaf spot, Leaf blotch and Leaf Blight Diseases such as    -   Alternaria diseases caused for example by Alternaria solani;    -   Cercospora diseases caused for example by Cercospora beticola;    -   Cladiosporium diseases caused for example by Cladiosporium        cucumerinum;    -   Cochliobolus diseases caused for example by Cochliobolus sativus        (Conidiaform: Drechslera, Syn: Helminthosporium) or Cochliobolus        miyabeanus;    -   Colletotrichum diseases caused for example by Colletotrichum        lindemuthianum;    -   Cycloconium diseases caused for example by Cycloconium        oleaginum;    -   Diaporthe diseases caused for example by Diaporthe citri;    -   Elsinoe diseases caused for example by Elsinoe fawcettii;    -   Gloeosporium diseases caused for example by Gloeosporium        laeticolor;    -   Glomerella diseases caused for example by Glomerella cingulata;    -   Guignardia diseases caused for example by Guignardia bidwellii;    -   Leptosphaeria diseases caused for example by Leptosphaeria        maculans and Leptosphaeria nodorum;    -   Magnaporthe diseases caused for example by Magnaporthe grisea;    -   Mycosphaerella diseases caused for example by Mycosphaerella        graminicola, Mycosphaerella arachidicola and Mycosphaerella        fijiensis;    -   Phaeosphaeria diseases caused for example by Phaeosphaeria        nodorum;    -   Pyrenophora diseases caused for example by Pyrenophora teres or        Pyrenophora tritici repentis;    -   Ramularia-diseases caused for example by Ramularia collo-cygni        or Ramularia areola;    -   Rhynchosporium diseases caused for example by Rhynchosporium        secalis; Septoria diseases caused for example by Septoria apii        and Septoria lycopersici;    -   Typhula diseases caused for example by Thyphula incarnate;    -   Venturia diseases caused for example by Venturia inaequalis;    -   Root-, Sheath and Stem Diseases such as    -   Corticium diseases caused for example by Corticium graminearum;    -   Fusarium diseases caused for example by Fusarium oxysporum;    -   Gaeumannomyces diseases caused for example by Gaeumannomyces        graminis;    -   Rhizoctonia diseases caused for example by Rhizoctonia solani;    -   Sarocladium diseases caused for example by Sarocladium oryzae;    -   Sclerotium diseases caused for example by Sclerotium oryzae;    -   Tapesia diseases caused for example by Tapesia acuformis;    -   Thielaviopsis diseases caused for example by Thielaviopsis        basicola;    -   Ear and Panicle Diseases including Maize cob such as    -   Alternaria diseases caused for example by Alternaria spp.;    -   Aspergillus diseases caused for example by Aspergillus flavus;    -   Cladosporium diseases caused for example by Cladiosporium        cladosporioides;    -   Claviceps diseases caused for example by Claviceps purpurea;    -   Fusarium diseases caused for example by Fusarium culmorum;    -   Gibberella diseases caused for example by Gibberella zeae;    -   Monographella diseases caused for example by Monographella        nivalis;    -   Smut- and Bunt Diseases such as    -   Sphacelotheca diseases caused for example by Sphacelotheca        reiliana;    -   Tilletia diseases caused for example by Tilletia caries;    -   Urocystis diseases caused for example by Urocystis occulta;    -   Ustilago diseases caused for example by Ustilago nuda;    -   Fruit Rot and Mould Diseases such as    -   Aspergillus diseases caused for example by Aspergillus flavus;    -   Botrytis diseases caused for example by Botrytis cinerea;    -   Penicillium diseases caused for example by Penicillium expansum        and Penicillium purpurogenum;    -   Rhizopus diseases caused by example by Rhizopus stolonifer    -   Sclerotinia diseases caused for example by Sclerotinia        sclerotiorum;    -   Verticillium diseases caused for example by Verticillium        alboatrum;    -   Seed- and Soilborne Decay, Mould, Wilt, Rot and Damping-off        diseases    -   Alternaria diseases caused for example by Alternaria        brassicicola;    -   Aphanomyces diseases caused for example by Aphanomyces        euteiches;    -   Ascochyta diseases caused for example by Ascochyta lentis;    -   Aspergillus diseases caused for example by Aspergillus flavus;    -   Cladosporium diseases caused for example by Cladosporium        herbarum;    -   Cochliobolus diseases caused for example by Cochliobolus        sativus;    -   (Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium);    -   Colletotrichum diseases caused for example by Colletotrichum        coccodes;    -   Fusarium diseases caused for example by Fusarium culmorum;    -   Gibberella diseases caused for example by Gibberella zeae;    -   Macrophomina diseases caused for example by Macrophomina        phaseolina;    -   Microdochium diseases caused for example by Microdochium nivale;    -   Monographella diseases caused for example by Monographella        nivalis;    -   Penicillium diseases caused for example by Penicillium expansum;    -   Phoma diseases caused for example by Phoma lingam;    -   Phomopsis diseases caused for example by Phomopsis sojae;    -   Phytophthora diseases caused for example by Phytophthora        cactorum;    -   Pyrenophora diseases caused for example by Pyrenophora graminea;    -   Pyricularia diseases caused for example by Pyricularia oryzae;    -   Pythium diseases caused for example by Pythium ultimum;    -   Rhizoctonia diseases caused for example by Rhizoctonia solani;    -   Rhizopus diseases caused for example by Rhizopus oryzae;    -   Sclerotium diseases caused for example by Sclerotium rolfsii;    -   Septoria diseases caused for example by Septoria nodorum;    -   Typhula diseases caused for example by Typhula incarnate;    -   Verticillium diseases caused for example by Verticillium        dahliae;    -   Canker, Broom and Dieback Diseases such as    -   Nectria diseases caused for example by Nectria galligena;    -   Blight Diseases such as    -   Monilinia diseases caused for example by Monilinia lexa;    -   Leaf Blister or Leaf Curl Diseases including deformation of        blooms and fruit such as    -   Exobasidium diseases caused for example by Exobasidium vexans.    -   Taphrina diseases caused for example by Taphrina deformans;    -   Decline Diseases of Wooden Plants such as    -   Esca disease caused for example by Phaeomoniella clamydospora,        Phaeoacremonium aleophilum and Fomitiporia mediterranea;    -   Ganoderma diseases caused by example by Ganoderma boninense;    -   Diseases of Flowers and Seeds such as    -   Botrytis diseases caused for example by Botrytis cinerea;    -   Diseases of Tubers such as    -   Rhizoctonia diseases caused for example by Rhizoctonia solani;    -   Helminthosporium diseases caused for example by Helminthosporium        solani;    -   Club root diseases such as    -   Plasmodiophora diseases, caused for example by Plamodiophora        brassicae;    -   Diseases caused by Bacterial Organisms such as    -   Xanthomanas species for example Xanthomonas campestris pv.        oryzae;    -   Pseudomonas species for example Pseudomonas syringae pv.        lachrymans;    -   Erwinia species for example Erwinia amylovora.

The fungicide composition according to the invention can also be usedagainst fungal diseases liable to grow on or inside timber. The term“timber” means all types of species of wood, and all types of working ofthis wood intended for construction, for example solid wood,high-density wood, laminated wood, and plywood. The method for treatingtimber according to the invention mainly consists in contacting one ormore compounds according to the invention, or a composition according tothe invention; this includes for example direct application, spraying,dipping, injection or any other suitable means.

The dose of active compound usually applied in the methods of treatmentaccording to the invention is generally and advantageously from 10 to800 g/ha, preferably from 50 to 300 g/ha for applications in foliartreatment. The dose of active substance applied is generally andadvantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to150 g per 100 kg of seed in the case of seed treatment.

It is clearly understood that the doses indicated herein are given asillustrative examples of the method according to the invention. A personskilled in the art will know how to adapt the application doses, notablyaccording to the nature of the plant or crop to be treated.

Furthermore combinations and compositions according to the invention mayalso be used to reduce the contents of mycotoxins in plants and theharvested plant material and therefore in foods and animal feed stuffmade therefrom.

Especially but not exclusively the following mycotoxins can bespecified:

Deoxynivalenole (DON), Nivalenole, 15-Ac-DON, 3-Ac-DON, T2-undHT2-Toxins, Fumonisines, Zearalenone Moniliformine, Fusarine,Diaceotoxyscirpenole (DAS), Beauvericine, Enniatine, Fusaroproliferine,Fusarenole, Ochratoxines, Patuline, Ergotalkaloides und

Aflatoxines, which are caused for example by the following fungaldiseases: Fusarium spec., like Fusarium acuminatum, F. avenaceum, F.crookwellense, F. culmorum, F. graminearum (Gibberella zeae), F.equiseti, F. fujikoroi, F. musarum, F. oxysporum, F. proliferatum, F.poae, F. pseudograminearum, F. sambucinum, F. scirpi, F. semitectum, F.solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F.tricinctum, F. verticillioides and others but also by Aspergillus spec.,Penicillium spec., Claviceps purpurea, Stachybotrys spec. and others.

The present invention therefore relates to the use of compounds offormula (I) as herein-described for the reduction of mycotoxins inplants and part of plants, and to methods of combating phytopathogenicand mycotoxin producing fungi characterized in that compounds of formula(I) as herein-described are applied to these fungi and/or their habitat.

The present invention therefore relates to the use of compounds offormula (I) as herein-described as insecticide, and/or nematicide.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants inwhich a heterologous gene has been stably integrated into the genome.The expression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for example,antisense technology, co suppression technology or RNAinterference—RNAi-technology). A heterologous gene that is located inthe genome is also called a transgene. A transgene that is defined byits particular location in the plant genome is called a transformationor transgenic event.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active compounds and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf color, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which exceed theeffects which were actually to be expected.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are also suitable for mobilizing the defense system ofthe plant against attack by unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses. This may, if appropriate, be one of thereasons of the enhanced activity of the combinations according to theinvention, for example against fungi. Plant-strengthening(resistance-inducing) substances are to be understood as meaning, in thepresent context, those substances or combinations of substances whichare capable of stimulating the defense system of plants in such a waythat, when subsequently inoculated with unwanted phytopathogenic fungiand/or microorganisms and/or viruses, the treated plants display asubstantial degree of resistance to these unwanted phytopathogenic fungiand/or microorganisms and/or viruses. In the present case, unwantedphytopathogenic fungi and/or microorganisms and/or viruses are to beunderstood as meaning phytopathogenic fungi, bacteria and viruses. Thus,the substances according to the invention can be employed for protectingplants against attack by the abovementioned pathogens within a certainperiod of time after the treatment. The period of time within whichprotection is effected generally extends from 1 to 10 days, preferably 1to 7 days, after the treatment of the plants with the active compounds.

Plants and plant cultivars which are preferably to be treated accordingto the invention include all plants which have genetic material whichimpart particularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstresses, i.e. said plants show a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Plants and plant cultivars which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, flooding,increased soil salinity, increased mineral exposure, ozon exposure, highlight exposure, limited availability of nitrogen nutrients, limitedavailability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to theinvention, are those plants characterized by enhanced yieldcharacteristics. Increased yield in said plants can be the result of,for example, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including but not limited to, early flowering, floweringcontrol for hybrid seed production, seedling vigor, plant size,internode number and distance, root growth, seed size, fruit size, podsize, pod or ear number, seed number per pod or ear, seed mass, enhancedseed filling, reduced seed dispersal, reduced pod dehiscence and lodgingresistance. Further yield traits include seed composition, such ascarbohydrate content, protein content, oil content and composition,nutritional value, reduction in anti-nutritional compounds, improvedprocessability and better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristic of heterosis or hybrid vigorwhich results in generally higher yield, vigor, health and resistancetowards biotic and abiotic stress factors. Such plants are typicallymade by crossing an inbred male-sterile parent line (the female parent)with another inbred male-fertile parent line (the male parent). Hybridseed is typically harvested from the male sterile plants and sold togrowers. Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling, i.e. the mechanical removal of the male reproductive organs(or males flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plantsit is typically useful to ensure that male fertility in the hybridplants is fully restored. This can be accomplished by ensuring that themale parents have appropriate fertility restorer genes which are capableof restoring the male fertility in hybrid plants that contain thegenetic determinants responsible for male-sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species (WO-1992/005251, WO-1995/009910, WO-1998/27806,WO-2005/002324, WO-2006/021972 and U.S. Pat. No. 6,229,072). However,genetic determinants for male sterility can also be located in thenuclear genome. Male sterile plants can also be obtained by plantbiotechnology methods such as genetic engineering. A particularly usefulmeans of obtaining male-sterile plants is described in WO-1989/10396 inwhich, for example, a ribonuclease such as barnase is selectivelyexpressed in the tapetum cells in the stamens. Fertility can then berestored by expression in the tapetum cells of a ribonuclease inhibitorsuch as barstar (e.g. WO-1991/002069).

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.Plants can be made tolerant to glyphosate through different means. Forexample, glyphosate-tolerant plants can be obtained by transforming theplant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphatesynthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutantCT7) of the bacterium Salmonella typhimurium (Comai et al., Science(1983), 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp.(Barry et al., Curr. Topics Plant Physiol. (1992), 7, 139-145), thegenes encoding a Petunia EPSPS (Shah et al., Science (1986), 233,478-481), a Tomato EPSPS (Gasser et al., J. Biol. Chem. (1988), 263,4280-4289), or an Eleusine EPSPS (WO-2001/66704). It can also be amutated EPSPS as described in for example EP-A 0837944, WO-2000/066746,WO-2000/066747 or WO-2002/026995. Glyphosate-tolerant plants can also beobtained by expressing a gene that encodes a glyphosate oxido-reductaseenzyme as described in U.S. Pat. No. 5,776,760 and U.S. Pat. No.5,463,175. Glyphosate-tolerant plants can also be obtained by expressinga gene that encodes a glyphosate acetyl transferase enzyme as describedin for example WO-2002/036782, WO-2003/092360, WO-2005/012515 andWO-2007/024782. Glyphosate-tolerant plants can also be obtained byselecting plants containing naturally-occurring mutations of theabove-mentioned genes, as described in for example WO-2001/024615 orWO-2003/013226. Other herbicide resistant plants are for example plantsthat are made tolerant to herbicides inhibiting the enzyme glutaminesynthase, such as bialaphos, phosphinothricin or glufosinate. Suchplants can be obtained by expressing an enzyme detoxifying the herbicideor a mutant glutamine synthase enzyme that is resistant to inhibition.One such efficient detoxifying enzyme is an enzyme encoding aphosphinothricin acetyltransferase (such as the bar or pat protein fromStreptomyces species). Plants expressing an exogenous phosphinothricinacetyltransferase are for example described in U.S. Pat. Nos. 5,561,236;5,648,477; 5,646,024; 5,273,894; 5,637,489; 5,276,268; 5,739,082;5,908,810 and 7,112,665.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase (HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes thatcatalyze the reaction in which para-hydroxyphenylpyruvate (HPP) istransformed into homogentisate. Plants tolerant to HPPD-inhibitors canbe transformed with a gene encoding a naturally-occurring resistant HPPDenzyme, or a gene encoding a mutated HPPD enzyme as described inWO-1996/038567, WO-1999/024585 and WO-1999/024586. Tolerance toHPPD-inhibitors can also be obtained by transforming plants with genesencoding certain enzymes enabling the formation of homogentisate despitethe inhibition of the native HPPD enzyme by the HPPD-inhibitor. Suchplants and genes are described in WO-1999/034008 and WO-2002/36787.Tolerance of plants to HPPD inhibitors can also be improved bytransforming plants with a gene encoding an enzyme prephenatedehydrogenase in addition to a gene encoding an HPPD-tolerant enzyme, asdescribed in WO-2004/024928.

Still further herbicide resistant plants are plants that are madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitorsinclude, for example, sulfonylurea, imidazolinone, triazolopyrimidines,pyrimidinyloxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides, as described for examplein Tranel and Wright, Weed Science (2002), 50, 700-712, but also, inU.S. Pat. Nos. 5,605,011, 5,378,824, 5,141,870, and 5,013,659. Theproduction of sulfonylurea-tolerant plants and imidazolinone-tolerantplants is described in U.S. Pat. Nos. 5,605,011; 5,013,659; 5,141,870;5,767,361; 5,731,180; 5,304,732; 4,761,373; 5,331,107; 5,928,937; and5,378,824; and international publication WO-1996/033270. Otherimidazolinone-tolerant plants are also described in for exampleWO-2004/040012, WO-2004/106529, WO-2005/020673, WO-2005/093093,WO-2006/007373, WO-2006/015376, WO-2006/024351, and WO-2006/060634.Further sulfonylurea- and imidazolinone-tolerant plants are alsodescribed in for example WO-2007/024782.

Other plants tolerant to imidazolinone and/or sulfonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding as described for examplefor soybeans in U.S. Pat. No. 5,084,082, for rice in WO-1997/41218, forsugar beet in U.S. Pat. No. 5,773,702 and WO-1999/057965, for lettuce inU.S. Pat. No. 5,198,599, or for sunflower in WO-2001/065922.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes anyplant containing at least one transgene comprising a coding sequenceencoding:

-   -   1) an insecticidal crystal protein from Bacillus thuringiensis        or an insecticidal portion thereof, such as the insecticidal        crystal proteins listed by Crickmore et al., Microbiology and        Molecular Biology Reviews (1998), 62, 807-813, updated by        Crickmore et al. (2005) at the Bacillus thuringiensis toxin        nomenclature, online at:        http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or        insecticidal portions thereof, e.g., proteins of the Cry protein        classes Cry1Ab, Cry1Ac, Cry1F, Cry2Ab, Cry3Aa, or Cry3Bb or        insecticidal portions thereof; or    -   2) a crystal protein from Bacillus thuringiensis or a portion        thereof which is insecticidal in the presence of a second other        crystal protein from Bacillus thuringiensis or a portion        thereof, such as the binary toxin made up of the Cry34 and Cry35        crystal proteins (Moellenbeck et al., Nat. Biotechnol. (2001),        19, 668-72; Schnepf et al., Applied Environm. Microbiol. (2006),        71, 1765-1774); or    -   3) a hybrid insecticidal protein comprising parts of different        insecticidal crystal proteins from Bacillus thuringiensis, such        as a hybrid of the proteins of 1) above or a hybrid of the        proteins of 2) above, e.g., the Cry1A.105 protein produced by        corn event MON98034 (WO-2007/027777); or    -   4) a protein of any one of 1) to 3) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes introduced into the        encoding DNA during cloning or transformation, such as the        Cry3Bb1 protein in corn events MON863 or MON88017, or the Cry3A        protein in corn event MIR604;    -   5) an insecticidal secreted protein from Bacillus thuringiensis        or Bacillus cereus, or an insecticidal portion thereof, such as        the vegetative insecticidal (VIP) proteins listed at:        http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html,        e.g., proteins from the VIP3Aa protein class; or    -   6) a secreted protein from Bacillus thuringiensis or Bacillus        cereus which is insecticidal in the presence of a second        secreted protein from Bacillus thuringiensis or B. cereus, such        as the binary toxin made up of the VIP1A and VIP2A proteins        (WO-1994/21795); or    -   7) a hybrid insecticidal protein comprising parts from different        secreted proteins from Bacillus thuringiensis or Bacillus        cereus, such as a hybrid of the proteins in 1) above or a hybrid        of the proteins in 2) above; or    -   8) a protein of any one of 1) to 3) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes introduced into the        encoding DNA during cloning or transformation (while still        encoding an insecticidal protein), such as the VIP3Aa protein in        cotton event COT102.

Of course, an insect-resistant transgenic plant, as used herein, alsoincludes any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 8. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 8, to expand the range oftarget insect species affected when using different proteins directed atdifferent target insect species, or to delay insect resistancedevelopment to the plants by using different proteins insecticidal tothe same target insect species but having a different mode of action,such as binding to different receptor binding sites in the insect.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

-   -   a. plants which contain a transgene capable of reducing the        expression and/or the activity of poly(ADP-ribose)polymerase        (PARP) gene in the plant cells or plants as described in        WO-2000/004173 or WO2006/045633 or    -   b. plants which contain a stress tolerance enhancing transgene        capable of reducing the expression and/or the activity of the        PARG encoding genes of the plants or plants cells, as described        e.g. in WO-2004/090140.    -   c. plants which contain a stress tolerance enhancing transgene        coding for a plant-functional enzyme of the nicotinamide adenine        dinucleotide salvage synthesis pathway including nicotinamidase,        nicotinate phosphoribosyltransferase, nicotinic acid        mononucleotide adenyl transferase, nicotinamide adenine        dinucleotide synthetase or nicotine amide        phosphoribosyltransferase as described e.g. in WO2006/032469 or        WO-2006/133827 or PCT/EP07/002,433.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage-stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as:

-   -   1) transgenic plants which synthesize a modified starch, which        in its physical-chemical characteristics, in particular the        amylose content or the amylose/amylopectin ratio, the degree of        branching, the average chain length, the side chain        distribution, the viscosity behaviour, the gelling strength, the        starch grain size and/or the starch grain morphology, is changed        in comparison with the synthesised starch in wild type plant        cells or plants, so that this is better suited for special        applications. Said transgenic plants synthesizing a modified        starch are disclosed, for example, in EP 0571427,        WO-1995/004826, EP 0719338, WO-1996/15248, WO-1996/19581,        WO-1996/27674, WO-1997/11188, WO-1997/26362, WO-1997/32985,        WO-1997/42328, WO-1997/44472, WO-1997/45545, WO-1998/27212,        WO-1998/40503, WO99/58688, WO-1999/58690, WO-1999/58654,        WO-2000/008184, WO-2000/008185, WO-2000/008175, WO-2000/28052,        WO-2000/77229, WO-2001/12782, WO-2001/12826, WO-2002/101059,        WO-2003/071860, WO-2004/056999, WO-2005/030942, WO-2005/030941,        WO-2005/095632, WO-2005/095617, WO-2005/095619, WO-2005/095618,        WO-2005/123927, WO-2006/018319, WO-2006/103107, WO-2006/108702,        WO-2007/009823, WO-2000/22140, WO-2006/063862, WO-2006/072603,        WO-2002/034923, EP 06090134.5, EP 06090228.5, EP 06090227.7, EP        07090007.1, EP 07090009.7, WO-2001/14569, WO-2002/79410,        WO-2003/33540, WO-2004/078983, WO-2001/19975, WO-1995/26407,        WO-1996/34968, WO-1998/20145, WO-1999/12950, WO-1999/66050,        WO-1999/53072, U.S. Pat. No. 6,734,341, WO-2000/11192,        WO-1998/22604, WO-1998/32326, WO-2001/98509, WO-2001/98509,        WO-2005/002359, U.S. Pat. Nos. 5,824,790, 6,013,861,        WO-1994/004693, WO-1994/009144, WO-1994/11520, WO-1995/35026,        WO-1997/20936.    -   2) transgenic plants which synthesize non starch carbohydrate        polymers or which synthesize non starch carbohydrate polymers        with altered properties in comparison to wild type plants        without genetic modification. Examples are plants producing        polyfructose, especially of the inulin and levan-type, as        disclosed in EP 0663956, WO-1996/001904, WO-1996/021023,        WO-1998/039460, and WO-1999/024593, plants producing alpha 1,4        glucans as disclosed in WO-1995/031553, US 2002/031826, U.S.        Pat. Nos. 6,284,479, 5,712,107, WO-1997/047806, WO-1997/047807,        WO-1997/047808 and WO-2000/014249, plants producing alpha-1,6        branched alpha-1,4-glucans, as disclosed in WO-2000/73422,        plants producing alternan, as disclosed in WO-2000/047727, EP        06077301.7, U.S. Pat. No. 5,908,975 and EP 0728213,    -   3) transgenic plants which produce hyaluronan, as for example        disclosed in WO-2006/032538, WO-2007/039314, WO-2007/039315,        WO-2007/039316, JP 2006/304779, and WO-2005/012529.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as cotton plants, with altered fibercharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants contain a mutation imparting such alteredfiber characteristics and include:

-   -   a) Plants, such as cotton plants, containing an altered form of        cellulose synthase genes as described in WO-1998/000549    -   b) Plants, such as cotton plants, containing an altered form of        rsw2 or rsw3 homologous nucleic acids as described in        WO2004/053219    -   c) Plants, such as cotton plants, with increased expression of        sucrose phosphate synthase as described in WO-2001/017333    -   d) Plants, such as cotton plants, with increased expression of        sucrose synthase as described in WO02/45485    -   e) Plants, such as cotton plants, wherein the timing of the        plasmodesmatal gating at the basis of the fiber cell is altered,        e.g. through downregulation of fiberselective β1,3-glucanase as        described in WO2005/017157    -   f) Plants, such as cotton plants, having fibers with altered        reactivity, e.g. through the expression of        N-acteylglucosaminetransferase gene including nodC and        chitinsynthase genes as described in WO2006/136351

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered oil profile characteristics. Such plants can beobtained by genetic transformation or by selection of plants contain amutation imparting such altered oil characteristics and include:

-   -   a) Plants, such as oilseed rape plants, producing oil having a        high oleic acid content as described e.g. in U.S. Pat. No.        5,969,169, 5,840,946 or 6,323,392 or 6,063,947    -   b) Plants such as oilseed rape plants, producing oil having a        low linolenic acid content as described in U.S. Pat. No.        6,270,828, 6,169,190 or 5,965,755    -   c) Plant such as oilseed rape plants, producing oil having a low        level of saturated fatty acids as described e.g. in U.S. Pat.        No. 5,434,283

Particularly useful transgenic plants which may be treated according tothe invention are plants which comprise one or more genes which encodeone or more toxins, such as the following which are sold under the tradenames YIELD GARD® (for example maize, cotton, soya beans), KnockOut®(for example maize), BiteGard® (for example maize), Bt-Xtra® (forexample maize), StarLink® (for example maize), Bollgard® (cotton),Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (for example maize),Protecta® and NewLeaf® (potato). Examples of herbicide-tolerant plantswhich may be mentioned are maize varieties, cotton varieties and soyabean varieties which are sold under the trade names Roundup Ready®(tolerance to glyphosate, for example maize, cotton, soya bean), LibertyLink® (tolerance to phosphinotricin, for example oilseed rape), IMI®(tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, forexample maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, orcombination of transformation events, that are listed for example in thedatabases from various national or regional regulatory agencies (see forexample http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

The compounds or mixtures according to the invention can also be usedfor the preparation of composition useful to curatively or preventivelytreat human or animal fungal diseases such as, for example, mycoses,dermatoses, trichophyton diseases and candidiases or diseases caused byAspergillus spp., for example Aspergillus fumigatus.

The various aspects of the invention will now be illustrated withreference to the following table of compound examples and the followingpreparation or efficacy examples.

Table 1 illustrates in a non-limiting manner examples of compounds offormula (I) according to the invention.

In table 1, M+H (Apcl+) means the molecular ion peak plus 1 a.m.u.(atomic mass unit) as observed in mass spectroscopy via positiveatmospheric pressure chemical ionisation.

In table 1, the log P values were determined in accordance with EECDirective 79/831 Annex V.A8 by HPLC (High Performance LiquidChromatography) on a reversed-phase column (C 18), using the methoddescribed below:

Temperature: 40° C.; Mobile phases: 0.1% aqueous formic acid andacetonitrile; linear gradient to from 10% acetonitrile to 90%acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (comprising 3to 16 carbon atoms) with known log P values (determination of the log Pvalues by the retention times using linear interpolation between twosuccessive alkanones). lambda-max-values were determined usingUV-spectra from 200 nm to 400 nm and the peak values of thechromatographic signals.

Table 2 provides the NMR data (¹H and/or ¹³C) of a selected number ofcompounds from table 1.

Mass Example X¹ X² T Z¹ Z² Z³ R¹ R² R³ R⁴ Y R⁵ logP M + H NMR  1 F F Ocyclopropyl H H CF₃ H H Cl CR⁵ H 3.8 426 table 2  2 F F O cyclopropyl HH CF₃ H H H CR⁵ Cl 3.46 426 table 2  3 F F O cyclopropyl H Htrimethylsilyl H H H CR⁵ H 4.36 396 table 2  4 F F O cyclopropyl H H BrH H Cl CR⁵ H 3.67 436 table 2  5 F F O cyclopropyl H H CF₃ H H Cl CR⁵ F3.62 444 table 2  6 F F O cyclopropyl H H propan-2-yl H H H CR⁵ H 3.35366 table 2  7 F F S cyclopropyl H H Cl H CF₃ H N 4.11 443  8 F F Ocyclopropyl H H I H H H CR⁵ F 3.26 468  9 F F O cyclopropyl H H I H H HCR⁵ H 3.37 450 table 2 10 F F O cyclopropyl H H Br H H F CR⁵ F 3.21 43811 F F O cyclopropyl H H trimethylsilyl H H H CR⁵ F 4.31 414 table 2 12F F O cyclopropyl H H CF₃ H H CH₃ CR⁵ H 3.78 406 13 F F O cyclopropyl HH ethyl(dimethyl) H H H CR⁵ H 4.75 410 silyl 14 F F O cyclopropyl H Htriethylsilyl H H H CR⁵ H 5.53 438 table 2 15 F F O cyclopropyl H H CF₃H H Cl CR⁵ Cl 3.89 460 16 F F O cyclopropyl H H Br H Br F CR⁵ H 3.96 49817 F F O cyclopropyl H H Br H CH₃ Br CR⁵ H 4.19 494 18 F F O cyclopropylH H Cl Cl H Cl CR⁵ H 4.11 426 19 F F O cyclopropyl H H I H H H CR⁵ Cl3.58 484 20 F F O cyclopropyl H H I H Cl H CR⁵ H 3.99 484 21 F F Ocyclopropyl H H I H H Br CR⁵ H 3.94 528 22 F F O cyclopropyl H CH₃ I H HH CR⁵ H 3.48 464  22a F F O cyclopropyl H CH₃ I H H H CR⁵ H Enantiomer(−)  22b F F O cyclopropyl H CH₃ I H H H CR⁵ H Enantiomer (+) 23 F F Ocyclopropyl H H I H H Cl CR⁵ H 3.83 484 24 F F O cyclopropyl H Htrimethylsilyl H H Cl CR⁵ H 4.81 430 table 2 25 F F O cyclopropyl H HCF₃ H Cl Cl CR⁵ H 4.34 26 F F O cyclopropyl H CH₃ pentyl H H H CR⁵ H4.92 408 27 F F O cyclopropyl H H pentyl H H H CR⁵ Cl 5 428 table 2 28 FF O cyclopropyl H H pentyl H H H CR⁵ H 4.62 394 29 F F O cyclopropyl H Hpropan-2-yl H H Cl CR⁵ H 4.09 400 table 2 30 F F O cyclopropyl H H(trifluoromethyl)- H H H CR⁵ H 3.74 424 table 2 sulfanyl 31 F F Ocyclopropyl H H 2-methylpropyl H Cl H CR⁵ H 4.59 414 32 F F Ocyclopropyl H H 2-methylpropyl H H H CR⁵ Cl 4.44 414 table 2 33 F F Ocyclopropyl H H 2-methylpropyl H H H CR⁵ H 4.15 380 table 2 34 Cl F Ocyclopropyl H H propan-2-yl H H H CR⁵ H 3.81 382 table 2 35 Cl F Ocyclopropyl H H I H H H CR⁵ H 3.6 466 table 2 36 Cl F O cyclopropyl H HCF₃ H H Cl CR⁵ H 4.01 442 table 2 37 Cl F O cyclopropyl H Htrimethylsilyl H H H CR⁵ H 4.49 412 table 2 38 F F S cyclopropyl H Htrimethylsilyl H H H CR⁵ H 4.94 412 table 2 39 F F S cyclopropyl H H H HH H CR⁵ H 3.44 340 table 2 40 F F O cyclopropyl H CH₃ H Cl H Cl CR⁵ H4.04 406 table 2  40a F F O cyclopropyl H CH₃ H Cl H Cl CR⁵ H Enantiomer(−)  40b F F O cyclopropyl H CH₃ H Cl H Cl CR⁵ H Enantiomer (+) 41 F F Ocyclopropyl H H cyclopropyl H H Cl CR⁵ H 3.87 398 table 2 42 F F Ocyclopropyl H —CH₂CH₂CH₂— H propan-2- H CR⁵ H 4.11 422 yloxy 43 F F Ocyclopropyl H H CF₃ H H I CR⁵ H 4.01 518 44 F F O cyclopropyl H CH₃—CH₂CH₂C(CH₃)₂CH₂— H H CR⁵ H 4.89 420  44a F F O cyclopropyl H CH₃—CH₂CH₂C(CH₃)₂CH₂— H H CR⁵ H Enantiomer (−) α_(D) = −0.026  44b F F Ocyclopropyl H CH₃ —CH₂CH₂C(CH₃)₂CH₂— H H CR⁵ H Enantiomer (+) α_(D) =+0.020 45 F F O cyclopropyl H H I H H Br CR⁵ F 3.8 546 46 F F Ocyclopropyl H CH₃ H CH₃ H CH₃ CR⁵ H 3.8 366 table 2  46a F F Ocyclopropyl H CH₃ H CH₃ H CH₃ CR⁵ H Enantiomer (−)  46b F F Ocyclopropyl H CH₃ H CH₃ H CH₃ CR⁵ H Enantiomer (+) 47 F F O cyclopropylH H cyclopropyl H H H CR⁵ H 3.44 364 48 F F O cyclopropyl H H ethyl H HH CR⁵ H 3.33 352 49 F F O cyclopropyl H H trimethylsilyl H H F CR⁵ F4.36 432 50 F F O cyclopropyl H CH₃ —CH₂CH(CH₃)CH₂CH₂— H H CR⁵ H 4.59406 51 F F O cyclopropyl H CH₃ —CH₂CH₂CH₂CH₂— H H CR⁵ H 4.14 392 52 F FO cyclopropyl H H CF₃ H H Br CR⁵ CF₃ 3.85 470 table 2 53 F F Ocyclopropyl H H ethyl H CH₃ CH₃ CR⁵ H 4.04 380 54 F F O cyclopropyl H Hcyclopropyl H H F CR⁵ F 3.51 400 55 Cl F O cyclopropyl H CH₃ CF₃ H H HCR⁵ H 3.64 422 56 Cl F O cyclopropyl H H CF₃ H H H CR⁵ H 3.58 408 57 ClF O cyclopropyl H H Cl H CF₃ H N 3.55 443 table 2 58 Cl F O cyclopropylH CH₃ Cl H Cl H N 3.69 423 59 Cl F O cyclopropyl H H Cl H Cl H CR⁵ H3.89 408 60 Cl F O cyclopropyl H CH₃ H H phenoxy H CR⁵ H 4.31 446 table2 61 F F O cyclopropyl H H CF₃ H H H CR⁵ H 3.39 392 62 F F O cyclopropylH CH₃ Cl H Cl H N 3.48 407 63 F F O cyclopropyl H H Cl H Cl H CR⁵ H 3.69392 64 F F O cyclopropyl H H H phenyl H H CR⁵ H 3.78 400 65 F F Ocyclopropyl H CH₃ H H phenoxy H CR⁵ H 4.14 430 66 F F O cyclopropyl HCH₃ CF₃ H H H CR⁵ H 3.42 406 67 Cl F O cyclopropyl H H H phenyl H H CR⁵H 3.94 416 68 F F O cyclopropyl H H CF₃ H H F CR⁵ F 3.31 428 69 F F Ocyclopropyl H ethyl Cl H Cl H CR⁵ H 4.2 420 table 2 70 F F O cyclopropylH CH₃ Cl H Cl H CR⁵ H 3.83 406 table 2 71 F F O cyclopropyl H ethyl H ClH Cl CR⁵ H 4.41 72 F F O cyclopropyl H CH₃ —OCF₂O— H H CR⁵ H 3.58 418 73F F O cyclopropyl H CH₃ —CH₂CHC(CH₃)₂— H t-Bu CR⁵ H 5.68 462 74 F F Ocyclopropyl H —(CH₂)₃— CH₃ H CH₃ CR⁵ H 4.25 392 75 F F O cyclopropyl H HBr H CH₃ F CR⁵ H 3.73 434 76 F F O cyclopropyl H H terbutyl H H H CR⁵ H4.06 380 77 F F O cyclopropyl H CH₃ H H Phenyl- H CR⁵ H 4.23 464 CF₂— 78F F O cyclopropyl H CH₃ H Phenyl- H H CR⁵ H 4.15 464 CF₂— 79 F F Ocyclopropyl H H Cl H CH₃ CH₃ CR⁵ H 3.85 386 80 F F O cyclopropyl H CH₃isopropyl H H H CR⁵ H 3.99 380 table 2 81 F F O cyclopropyl H CH₃ ethylH H H CR⁵ H 3.69 366 table 2 82 F F O cyclopropyl H H cyclopentyl H H HCR⁵ H 4.2 392 table 2 83 F F O cyclopropyl H H Br H H H CR⁵ Cl 3.42 43684 F F O cyclopropyl H H CF₃ H H H CR⁵ F 410 table 2 85 F F Ocyclopropyl H —CH₂C(CH₃)₂— H H H CR⁵ H 3.87 378 86 F F O cyclopropyl H—CH₂CH₂O— H H H CR⁵ H 2.84 366 87 F F O cyclopropyl H H Br —O—CH₂—O— BrCR⁵ H 3.44 524 88 F F O cyclopropyl H H ethyl H H H CR⁵ ethyl 4.01 38089 F F O cyclopropyl H H Cl H CF₃ H CR⁵ Cl 4.06 460 table 2 90 F F Ocyclopropyl H CH₃ Cl H CF₃ H N 3.71 441 table 2 91 F F O cyclopropyl HCH₃ OCF₃ H H H CR⁵ H 3.6 422 92 F F O cyclopropyl H H Br H H H CR⁵ Br3.51 480 93 F F O cyclopropyl H butyl H H CF₃ H CR⁵ H 4.8 448 94 F F Ocyclopropyl H butyl H H H H CR⁵ H 4.26 380 95 F F O cyclopropyl H CH₃ HH H H CR⁵ H 3.06 338 96 F F O cyclopropyl H CH₃ Cl H H CF₃ CR⁵ H 3.89440 97 F F O cyclopropyl H —(CH₂)₃— H H H CR⁵ Br 3.78 442 98 F F Ocyclopropyl H CH₃ Br H H H CR⁵ H 3.31 416 99 F F O cyclopropyl H—CH₂CH₂CMe₂— H H H CR⁵ H 4.16 392 100  F F O cyclopropyl H —CHBuCH₂— H HH CR⁵ H 4.85 406 101  F F O cyclopropyl H CH₃ CF3 H H Cl CR⁵ H 3.92 440102  F F O cyclopropyl H —CH₂CH₂— CH₃ H H CR⁵ H 3.55 364 103  F F Ocyclopropyl H CH₃ H I H H CR⁵ H 3.76 464 104  F F O cyclopropyl H H ClCF₃ H H CR⁵ H 3.64 426 105  F F O cyclopropyl H H OCF₃ H H H CR⁵ H 3.46408 106  F F O cyclopropyl H CH₃ H Br H Br CR⁵ H 4.26 494 107  F F Ocyclopropyl H H Cl H Cl H CR⁵ Cl 3.99 426 108  F F O cyclopropyl H H CH₃H H H CR⁵ CH₃ 3.31 352 109  F F O cyclopropyl H —CH₂CH₂— H H H CR⁵ Cl3.42 384 110  F F O cyclopropyl H H 4-fluoro- H H H CR⁵ H 3.85 434phenoxy 111  F F O cyclopropyl H H ethyl H H F CR⁵ F table 2 112  F F Ocyclopropyl H H 2-methyl-propyl H H F CR⁵ F table 2 113  F F Ocyclopropyl H H cyclopropyl H H H CR⁵ Cl table 2 114  F F O cyclopropylH H ethyl H H F CR⁵ H table 2 115  F F O cyclopropyl H H butyl H H H CR⁵Cl table 2 116  F F O cyclopropyl H H trimethylsilyl H H H CR⁵ Cl table2 117  F F O cyclopropyl H H CF₃ H H F CR⁵ CF3 table 2 118  F F Ocyclopropyl H H trimethylsilyl H H F CR⁵ H table 2 119  F F Ocyclopropyl H H butyl H H Cl CR⁵ H table 2 120  F F O cyclopropyl H H2-methyl-propyl H H Cl CR⁵ H table 2 121  F F O cyclopropyl H H butyl HH F CR⁵ H table 2 122  F F O cyclopropyl H H 2-methyl-propyl H H F CR⁵ Htable 2 123  F F O cyclopropyl H H cyclopropyl H H F CR⁵ H table 2 124 F F O cyclopropyl H H ethyl H H H CR⁵ Cl table 2 125  F F O cyclopropylH H ethyl H H Cl CR⁵ H table 2 126  F F O cyclopropyl H H butyl H H FCR⁵ F table 2 127  F F O cyclopropyl H H 2-methyl-propyl H H H CR⁵ Ftable 2 128  F F O cyclopropyl H H butyl H H H CR⁵ F table 2 129  F F Ocyclopropyl H H ethyl H H H CR⁵ F table 2 130  F F O cyclopropyl H Hcyclopropyl H H H CR⁵ F table 2 131  F F S cyclopropyl H H propan-2-yl HH H CR⁵ H 4.36 382 table 2 132  F F S cyclopropyl H H Cl H H H CR⁵ CF₃4.23 442 133  F F S cyclopropyl H H ethyl H H H CR⁵ H 4.06 134  F F Ocyclopropyl H H propan-2-yl H H H CR⁵ F 135  F F O cyclopropyl H Hpropan-2-yl H H F CR⁵ H table 2 136  F F O cyclopropyl H H propan-2-yl HH F CR⁵ F table 2 137  F F O cyclopropyl H H cyclopentyl H H H CR⁵ Ftable 2 138  F F O cyclopropyl H H cyclopentyl H H F CR⁵ H table 2 139 F F O cyclopropyl H H cyclopentyl H H F CR⁵ F table 2 140  F F Ocyclopropyl H H cyclopentyl H H Cl CR⁵ H table 2 141  F F O cyclopropylH H cyclopentyl H H H CR⁵ Cl table 2 142  F F O 2-methyl- H H ethyl H HH CR⁵ H table 2 cyclopropyl 143  F F O 2-methyl- H H trimethylsilyl H HH CR⁵ H table 2 cyclopropyl 144  F F O 2-methyl- H H CF₃ H H H CR⁵ Cltable 2 cyclopropyl 145  Cl F O cyclopropyl H H ethyl H H Cl CR⁵ H 146 Cl F O cyclopropyl H H propan-2-yl H H F CR⁵ H 3.92 400 147  Cl F Ocyclopropyl H H CF₃ H H F CR⁵ H 148  Cl F O cyclopropyl H H butyl H H ClCR⁵ H 149  Cl F O cyclopropyl H H 2-Methyl-propyl H H Cl CR⁵ H 150  Cl FO cyclopropyl H H 2-Methyl-propyl H H H CR⁵ Cl 4.74 430 151  Cl F Ocyclopropyl H H trimethylsilyl H H H CR⁵ Cl 4.82 446 152  Cl F Ocyclopropyl H H cyclopentyl H H Cl CR⁵ H 4.92 442 153  Cl F Ocyclopropyl H H cyclopropyl H H F CR⁵ H 154  F F O cyclopropyl H H1,3-dimethyl- H H H CR⁵ H 4.82 408 butyl 155  F F O cyclopropyl H H2-cyclopropyl- H H H CR⁵ H 4.25 404 cyclopropyl 156  F F O cyclopropyl HH butan-2-yl H H H CR⁵ H 4.06 380 157  F F O 2-methyl- H H propan-2-yl HH H CR⁵ H table 2 cyclopropyl

TABLE 2 Example NMR 1 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 8.76, 22.87,30.58, 34.78, 36.95, 47.27, 107.72, 110.08, 112.44, 127.40, 127.53,127.59, 127.65, 127.70, 128.24 2 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 9.05,28.31, 34.71, 44.60, 107.24, 109.61, 111.97, 125.25, 125.31, 125.37,128.95, 133.99 3 ¹H NMR (400 MHz, DMSO-d6) δ ppm: 0.36 (s, 9H), 0.53(bs, 2H) 0.64 (d, 2H), 2.86 (bs, 1H), 3.82 (bs, 3H), 4.77 (bs, 2H), 7.00(t, J = 54.06 Hz, 1H), 7.11-7.49 (m, 4H) ¹³C NMR (400 MHz, DMSO-d6) δppm: 0.00, 8.62, 30.24, 34.54, 50.84, 109.78, 124.83, 126.08, 129.44,134.48 4 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 9.07, 34.76, 51.10, 107.61,109.98, 112.34, 129.02, 129.16, 133.99 5 ¹³C NMR (400 MHz, DMSO-d6) δppm: 9.08, 28.78, 34.72, 41.48, 107.28, 109.65, 112.01, 122.52, 122.57,122.62, 130.05 6 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 9.15, 23.73, 28.59,29.60, 34.72, 47.82, 107.48, 109.85, 112.21, 125.54, 125.71, 127.96,129.07 9 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 9.04, 34.74, 109.92, 112.28,128.45, 128.66, 129.10, 139.67 11 ¹³C NMR (400 MHz, DMSO-d6) δ ppm:−0.00, 8.51, 34.04, 115.94, 116.17, 128.02, 128.10, 129.86, 129.90 14¹³C NMR (400 MHz, DMSO-d6) δ ppm: 4.17, 4.43, 7.57, 8.73, 34.72, 51.00,124.80, 126.09, 128.64, 129.46, 135.84 24 ¹³C NMR (400 MHz, DMSO-d6) δppm: 0.00, 8.78, 30.25, 34.70, 50.63, 109.97, 125.22, 126.35, 135.99 27¹³C NMR (400 MHz, DMSO-d6) δ ppm: 9.21, 13.99, 22.58, 28.48, 31.17,31.67, 33.18, 34.69, 107.33, 109.69, 112.05, 127.58, 128.11, 128.79 29¹³C NMR (400 MHz, DMSO-d6) δ ppm: 8.62, 9.17, 23.62, 28.33, 29.78,30.32, 34.75, 45.79, 107.52, 109.89, 112.25, 127.10, 127.94, 128.50 30¹³C NMR (400 MHz, DMSO-d6) δ ppm: 8.82, 34.73, 107.64, 110.00, 112.37,128.33, 128.68, 131.87, 138.63 32 ¹³C NMR (400 MHz, DMSO-d6) δ ppm:9.15, 22.36, 28.47, 30.33, 34.70, 42.34, 44.62, 107.34, 109.71, 112.07,127.73, 128.48, 129.14 33 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 8.96, 22.53,29.70, 34.70, 41.79, 107.55, 109.92, 112.28, 126.12, 127.03, 127.89,130.50 34 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 23.72, 28.59, 36.91, 110.27,125.33, 125.73, 127.81, 128.74 35 ¹³C NMR (400 MHz, DMSO-d6) δ ppm:6.25, 8.79, 30.78, 36.94, 37.17, 55.89, 108.01, 110.37, 112.72, 128.33,128.49, 129.04, 139.55 36 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 5.91, 8.46,30.89, 36.95, 46.94, 108.16, 110.51, 112.87, 127.31, 127.47, 127.52,128.26 37 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: −0.00, 5.57, 8.21, 30.63,36.68, 50.76, 110.17, 125.13, 125.97, 129.31, 134.32 38 ¹H NMR (250 MHz,DMSO-d6) δ ppm: 0.37 (s, 9H), 0.54-0.74 (m, 4H), 3.11 (bs, 1H), 3.83 (s,3H), 5.41 (bs, 2H), 7.14 (t, J = 54.40 Hz, 1H), 7.04-7.51 (m, 4H) 39 ¹³CNMR (400 MHz, DMSO-d6) δ ppm: 0.01, 10.10, 34.69, 34.99, 35.04, 58.78,107.56, 109.93, 112.30, 127.24, 127.68, 127.76, 127.99, 128.71, 128.9140 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 7.30, 9.01, 17.02, 27.64, 27.70,34.70, 34.81, 53.95, 110.16, 112.53, 125.52, 127.40 41 ¹³C NMR (400 MHz,DMSO-d6) δ ppm: 7.27, 7.34, 9.09, 12.40, 34.76, 127.45, 127.51, 127.8342 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 6.38, 9.65, 21.96, 22.05, 22.15,22.51, 23.39, 28.15, 29.97, 30.17, 34.67, 38.91, 69.69, 69.97, 107.86,110.22, 112.58, 113.96, 114.07, 114.19, 115.86, 127.64, 129.67 44 ¹³CNMR (400 MHz, DMSO-d6) δ ppm: 7.81, 8.71, 18.51, 22.67, 26.36, 27.40,27.46, 29.20, 34.68, 35.79, 44.18, 52.33, 109.87, 125.14, 125.21, 129.4946 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 7.11, 8.73, 17.30, 21.41, 27.39,30.31, 34.65, 54.44, 107.77, 110.13, 112.49, 124.70, 128.69 51 ¹³C NMR(400 MHz, DMSO-d6) δ ppm: 7.88, 8.72, 18.57, 22.83, 23.20, 25.36, 27.48,27.54, 30.21, 34.67, 52.31, 107.50, 109.86, 112.22, 124.99, 125.22,129.04 52 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 8.75, 30.53, 34.77, 47.19,107.72, 110.08, 112.45, 127.62, 127.67, 127.73, 127.79, 130.44, 131.2157 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 8.60, 9.03, 31.42, 36.96, 37.06,45.71, 50.78, 107.59, 109.94, 112.30, 134.02, 143.88 60 ¹³C NMR (400MHz, DMSO-d6) δ ppm: 6.94, 8.03, 8.45, 17.15, 27.56, 36.86, 108.19,110.55, 112.90, 118.54, 118.91, 123.31, 128.48, 129.76 69 ¹³C NMR (400MHz, DMSO-d6) δ ppm: 8.17, 9.07, 11.13, 25.05, 28.79, 28.86, 34.62,34.83, 60.09, 107.53, 108.88, 109.88, 112.24, 126.89, 129.62, 130.55 70¹³C NMR (400 MHz, DMSO-d6) δ ppm: 8.16, 8.75, 18.18, 28.48, 28.55,34.64, 53.99, 107.45, 109.82, 112.18, 126.88, 129.44, 130.23 72 ¹³C NMR(400 MHz, DMSO-d6) δ ppm: 4.80, 7.92, 8.91, 17.35, 28.63, 28.70, 34.66,52.64, 52.80, 107.55, 108.56, 109.90, 112.26, 122.21, 122.73, 123.45,124.01 73 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 7.92, 8.40, 17.76, 27.38,27.45, 27.77, 28.45, 28.82, 31.62, 31.65, 31.71, 34.65, 34.82, 41.42,41.56, 53.62, 107.49, 108.88, 109.86, 112.22 74 ¹³C NMR (400 MHz,DMSO-d6) δ ppm: 6.42, 9.75, 19.69, 20.89, 21.01, 22.38, 22.73, 26.52,27.52, 28.24, 34.67, 56.32, 107.94, 110.30, 112.66, 124.34, 129.04 80¹³C NMR (400 MHz, DMSO-d6) δ ppm: 1.03, 8.06, 8.53, 8.84, 18.56, 22.97,25.17, 27.46, 27.53, 27.89, 34.65, 34.77, 45.72, 51.59, 107.50, 109.87,112.23, 125.33, 125.58, 127.93, 128.19 81 ¹³C NMR (400 MHz, DMSO-d6) δppm: 8.03, 8.82, 14.76, 18.50, 24.30, 27.42, 27.49, 29.71, 34.64, 52.06,107.53, 109.88, 112.24, 125.49, 127.84, 127.95, 128.19 82 ¹³C NMR (400MHz, DMSO-d6) δ ppm: 6.79, 9.11, 25.72, 25.85, 34.45, 34.56, 34.73,40.63, 58.46, 109.87, 112.24, 125.63, 126.14, 127.80, 128.64 84 ¹H NMR(300 MHz, CHCl3-d) δ ppm: 0.60-0.64 (m, 4H), 2.51 (bs, 1H), 3.79 (s,3H), 4.97 (s, 2H), 6.91 (t, J = 54.4 Hz, 1H), 7.27-7.33 (m, 1H),7.39-7.46 (m, 1H), 7.52 (d, 1H). ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 8.99,34.69, 109.64, 119.55, 119.79, 122.28, 129.53, 129.62 87 ¹³C NMR (400MHz, DMSO-d6) δ ppm: 9.14, 31.44, 34.75, 36.50, 102.00, 109.92, 125.6389 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 9.24, 34.74, 109.66, 125.55, 125.5990 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 8.63, 9.24, 9.44, 16.76, 27.55,27.62, 34.69, 45.80, 55.51, 109.68, 134.31, 143.61, 143.65 111 ¹H NMR(300 MHz, CHCl3-d): d 0.64 (d, 4H), 1.21 (t, 3H), 2.50 (bs, 1H), 2.64(q, 2H), 3.79 (s, 3H), 4.81 (s, 2H), 6.87 (t, J = 54.4 Hz, 1H),6.96-7.09 (m, 2H). 112 ¹H NMR (300 MHz, CHCl3-d): d 0.64 (d, 4H), 0.90(d, 6H), 1.79-1.83 (m, 1H), 2.55 (m, 3H), 3.79 (s, 3H), 4.79 (s, 2H),6.87 (t, J = 54.4 Hz, 1H), 6.89-7.06 (m, 2H). 113 ¹H NMR (300 MHz,CHCl3-d): d 0.56-0.58 (m, 2H), 0.66-0.70 (m, 4H), 0.92-0.99 (m, 2H),1.98-2.01 (m, 1H), 2.39 (bs, 1H), 3.79 (s, 3H), 5.12 (s, 2H), 6.93 (t, J= 54.4 Hz, 1H), 6.87-7.23 (m, 3H). 114 ¹H NMR (300 MHz, CHCl3-d): d0.65-0.66 (m, 4H), 1.21 (t, 3H), 2.62 (q, 2H), 2.64 (bs, 1H), 3.81 (s,3H), 4.71 (s, 2H), 6.86 (t, J = 54.6 Hz, 1H), 6.89-6.95 (m, 2H),7.13-7.18 (m, 1H). 115 ¹H NMR (300 MHz, CHCl3-d): d 0.53-0.60 (m, 4H),0.90 (t, 3H), 1.31-1.38 (m, 2H), 1.48-1.57 (m, 2H), 2.37 (bs, 1H),2.69-2.74 (m, 2H), 3.79 (s, 3H), 4.90 (s, 2H), 6.93 (t, J = 54.6 Hz,1H), 7.12-7.21 (m, 3H). 116 ¹H NMR (300 MHz, CHCl3-d): d 0.35 (s, 9H),0.46 (m, 4H), 2.58 (bs, 1H), 3.80 (s, 3H), 4.92 (s, 2H), 6.92 (t, J =54.7 Hz, 1H), 7.10-7.43 (m, 3H). 117 ¹H NMR (300 MHz, CHCl3-d): d0.62-0.70 (m, 4H), 2.89 (bs, 1H), 3.83 (s, 3H), 4.92 (s, 2H), 6.84 (t, J= 54.6 Hz, 1H), 7.02-7.25 (m, 2H), 7.64-7.69 (m, 1H). 118 ¹H NMR (300MHz, CHCl3-d): d 0.36 (s, 9H), 0.56-0.65 (m, 4H), 2.90 (bs, 1H), 3.83(s, 3H), 4.86 (s, 2H), 6.68-7.04 (m, 3H), 7.44-7.49 (m, 1H). ¹³C NMR(400 MHz, DMSO-d6) δ ppm: −0.00, 8.64, 34.60, 50.68, 109.84, 112.13,112.34, 112.89, 113.09, 136.43, 136.50 119 ¹H NMR (300 MHz, CHCl3-d): d0.65-0.68 (m, 4H), 0.92 (t, 3H), 1.33-1.40 (m, 2H), 1.49-1.54 (m, 2H),2.60 (t, 2H), 2.65 (bs, 1H), 3.81 (s, 3H), 4.71 (s, 2H), 6.85 (t, J =54.6 Hz, 1H), 7.04-7.20 (m, 3H). 120 ¹H NMR (300 MHz, CHCl3-d): d0.64-0.65 (m, 4H), 0.92 (d, 6H), 1.80-1.84 (m, 1H), 2.50 (d, 2H), 2.74(bs, 1H), 3.81 (s, 3H), 4.71 (s, 2H), 6.85 (t, J = 54.6 Hz, 1H),7.05-7.18 (m, 3H). 121 ¹H NMR (300 MHz, CHCl3-d): d 0.64-0.66 (m, 4H),0.92 (t, 3H), 1.33-1.41 (m, 2H), 1.49-1.54 (m, 2H), 2.60 (t, 2H), 2.74(bs, 1H), 3.81 (s, 3H), 4.71 (s, 2H), 6.86 (t, J = 54.6 Hz, 1H),6.87-6.92 (m, 2H), 7.04-7.12 (m, 1H). 122 ¹H NMR (300 MHz, CHCl3-d): d0.63-0.67 (m, 4H), 0.93 (d, 6H), 1.79-1.83 (m, 1H), 2.50 (d, 2H), 2.76(bs, 1H), 3.81 (s, 3H), 4.71 (s, 2H), 6.67-7.07 (m, 4H). 123 ¹H NMR (300MHz, CHCl3-d): d 0.60-0.66 (m, 6H), 0.89-0.95 (m, 2H), 1.82-1.84 (m,1H), 2.73 (bs, 1H), 3.81 (s, 3H), 4.89 (s, 2H), 6.68-6.99 (m, 4H). 124¹H NMR (300 MHz, CHCl3-d): d 0.52-0.62 (m, 4H), 1.21 (t, 3H), 2.37 (bs,1H), 2.75 (q, 2H), 3.79 (s, 3H), 4.93 (s, 2H), 6.93 (t, J = 54.4 Hz,1H), 7.11-7.20 (m, 3H). 125 ¹H NMR (300 MHz, CHCl3-d): d 0.65-0.69 (m,4H), 1.21 (t, 3H), 2.62-2.64 (m, 3H), 3.81 (s, 3H), 4.70 (s, 2H), 6.85(t, J = 54.6 Hz, 1H), 7.04-7.22 (m, 3H). 126 ¹H NMR (300 MHz, CHCl3-d):d 0.65 (d, 4H), 0.88 (t, 3H), 1.29-1.37 (m, 2H), 1.46-1.54 (m, 2H), 2.51(bs, 1H), 2.63 (t, 2H), 3.79 (s, 3H), 4.80 (s, 2H), 6.88 (t, J = 54.6Hz, 1H), 6.90-7.03 (m, 2H). 127 ¹H NMR (300 MHz, DMSO-d6): d 0.54-0.57(m, 4H), 0.82 (d, 6H), 1.73-1.78 (m, 1H), 2.33 (bs, 1H), 2.54 (d, 2H),3.75 (s, 3H), 4.68 (s, 2H), 6.76-7.12 (m, 3H), 7.23-7.30 (m, 1H). 128 ¹HNMR (300 MHz, CHCl3-d): d 0.55-0.62 (m, 4H), 0.89 (t, 3H), 1.25-1.42 (m,2H), 1.49-1.54 (m, 2H), 2.46 (bs, 1H), 2.67 (t, 2H), 3.78 (s, 3H), 4.79(s, 2H), 6.89 (t, J = 54.5 Hz, 1H), 6.88-7.07 (m, 2H), 7.17-7.22 (m,1H). 129 ¹H NMR (300 MHz, CHCl3-d): d 0.60-0.64 (m, 4H), 1.20 (t, 3H),2.50 (bs, 1H), 2.68 (q, 2H), 3.78 (s, 3H), 4.80 (s, 2H), 6.71-7.07 (m,3H), 7.22-7.23 (m, 1H). 130 ¹H NMR (300 MHz, CHCl3-d): d 0.59-0.61 (m,2H), 0.65-0.70 (m, 4H), 0.91-0.97 (m, 2H), 1.96 (bs, 1H), 2.44 (bs, 1H),3.79 (s, 3H), 4.96 (s, 2H), 6.89 (t, J = 54.6 Hz, 1H), 6.72-7.23 (m,3H). 131 ¹³C NMR (400 MHz, DMSO-d6) δ ppm: 10.41, 23.67, 28.95, 34.71,34.99, 35.04, 56.09, 109.77, 112.14, 125.52, 125.79, 126.07, 128.12,128.29, 128.46 135 ¹H NMR (300 MHz, CHCl3-d): d 0.65-0.69 (m, 4H), 1.22(d, 6H), 2.69 (bs, 1H), 3.10-3.14 (m, 1H), 3.81 (s, 3H), 4.75 (s, 2H),6.86 (t, J = 54.6 Hz, 1H), 6.88-6.93 (m, 2H), 7.23-7.28 (m, 1H). 136 ¹HNMR (300 MHz, CHCl3-d): d 0.66 (d, 4H), 1.19 (d, 6H), 2.47 (bs, 1H),3.12-3.19 (m, 1H), 3.78 (s, 3H), 4.83 (s, 2H), 6.89 (t, J = 54.6 Hz,1H), 7.03-7.13 (m, 2H). 137 ¹H NMR (300 MHz, CHCl3-d): d 0.59-0.62 (m,4H), 1.56-1.63 (m, 2H), 1.65-1.75 (m, 2H), 1.76-1.82 (m, 2H), 1.95-2.02(m, 2H), 2.41-2.44 (m, 1H), 3.22-3.27 (m, 1H), 3.79 (s, 3H), 4.84 (s,2H), 6.89 (t, J = 52.5 Hz, 1H), 6.86-7.26 (m, 3H). 138 ¹H NMR (300 MHz,CHCl3-d): d 0.64-0.68 (m, 4H), 1.56-1.62 (m, 2H), 1.62-1.70 (m, 2H),1.76-1.83 (m, 2H), 1.96-2.05 (m, 2H), 2.71 (bs, 1H), 3.13-3.19 (m, 1H),3.81 (s, 3H), 4.76 (s, 2H), 6.86 (t, J = 54.6 Hz, 1H), 6.87-6.97 (m,2H), 7.23-7.28 (m, 1H). 139 ¹H NMR (300 MHz, CHCl3-d): d 0.62-0.64 (d,4H), 1.56-1.61 (m, 2H), 1.62-1.68 (m, 2H), 1.70-1.83 (m, 2H), 1.94-2.04(m, 2H), 2.47 (bs, 1H), 3.17-3.23 (m, 1H), 3.79 (s, 3H), 4.84 (s, 2H),6.88 (t, J = 54.6 Hz, 1H), 7.04-7.11 (m, 2H). 140 ¹H NMR (300 MHz,CHCl3-d): d 0.65-0.69 (m, 4H), 1.56-1.62 (m, 2H), 1.66-1.73 (m, 2H),1.78-1.83 (m, 2H), 1.96-2.03 (m, 2H), 2.70 (bs, 1H), 3.14-3.19 (m, 1H),3.81 (s, 3H), 4.75 (s, 2H), 6.86 (t, J = 54.6 Hz, 1H), 7.18-7.23 (m,3H). 141 ¹H NMR (300 MHz, CHCl3-d): d 0.56-0.58 (m, 4H), 1.56-1.63 (m,2H), 1.65-1.72 (m, 2H), 1.78-1.81 (m, 2H), 2.00-2.02 (m, 2H), 2.39 (bs,1H), 3.28-3.33 (m, 1H), 3.79 (s, 3H), 4.98 (s, 2H), 6.93 (t, J = 54.4Hz, 1H), 7.12-7.26 (m, 3H). 142 ¹H NMR (300 MHz, DMSO-d6): δ 0.43 (q,1H), 0.68 (d, 3H), 0.60-0.80 (m, 1H), 0.90-1.00 (m, 1H), 1.16 (t, 3H),2.15-2.35 (m, 1H), 2.62 (q, 2H), 3.80 (s, 3H), 4.51 (d, 1H), 4.77 (d,1H), 6.98 (t, J = 53.8 Hz, 1H), 7.10-7.30 (m, 4H). 143 ¹H NMR (300 MHz,DMSO-d6): δ 0.35 (s, 9H), 0.35-0.45 (m, 1H), 0.60-0.70 (m, 4H),0.80-0.95 (m, 1H), 3.83 (s, 3H), 4.61 (d, 1H), 4.87 (d, 1H), 6.99 (t, J= 53.7 Hz, 1H), 7.10 (d, 1H) 7.25 (t, 1H) 7.38 (t, 1H) 7.49 (d, 1H). 144¹H NMR (300 MHz, DMSO-d6): δ 0.31-0.33 (m, 1H), 0.53 (d, 3H), 0.66-0.67(m, 1H), 0.80 (m, 1H), 2.01 (bs, 1H), 3.77 (s, 3H), 4.83-4.98 (m, 2H),6.95 (t, J = 53.8 Hz, 1H), 7.59 (t, 1H) 7.79-7.82 (m, 2H). 157 ¹H NMR(300 MHz, DMSO-d6): d 0.41-0.43 (m, 1H), 0.65-0.67 (m, 3H), 0.74-0.78(m, 1H), 0.80-0.86 (m, 1H), 1.14 (m, 6H), 2.14-2.16 (m, 1H), 3.10 (bs,1H), 3.78 (s, 3H), 4.48-4.81 (m, 2H), 6.96 (t, J = 53.8 Hz, 1H),7.13-7.20 (m, 4H).

The following examples illustrate in a non limiting manner thepreparation and efficacy of the compounds of formula (I) according tothe invention.

Synthesis of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid(example IIb-1)

In a 500 ml flask, 6.0 g (31 mmol) of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde wereadded to 30 ml of toluene. A solution of 2.4 g (62 mmol) of sodiumhydroxide in 6 ml of water was added to the reaction mixture, followedby 103 ml of a 30% solution of hydrogen peroxide in water, whilstkeeping the temperature below 37° C. After the end of the addition, thereaction mixture was stirred at 50° C. for 7 hours. Once the reactionmixture was back to room temperature, the two phases were separated andthe organic phase was extracted with 100 ml of water. The combinedaqueous phases were acidified to pH 2 with aqueous hydrochloric acid.The resulting white precipitate was filtered, washed with 2*20 ml ofwater, and dried to yield 3.2 g of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid as awhite solid.

¹H NMR (400 MHz, DMSO-d₆) δ ppm: 3.78 (s, 3H); 7.12 (t, 1H, J_(HF)=53.60Hz) 13.19 (s, 1H); IR (KBr): 1688 cm⁻¹(C═O); 2200-3200 cm⁻¹ broad(hydrogen bond);

Synthesis of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride (example IIC-1)

3.2 g of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylicacid and 44.3 ml of thionyl chloride were refluxed for 5 hours. Aftercooling down, the reaction mixture was evaporated under vacuum to yield3.5 g of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride as a yellow oil.

¹H NMR (400 MHz, CHCl₃-d₆) δ ppm: 3.97 (s, 3H); 7.00 (t, J=52.01 Hz, 1H); IR (TQ): 1759 and 1725 cm⁻¹(C═O);

Synthesis of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonylfluoride (example IId-1)

To a dried solution of 4.0 g (70 mmol) of potassium fluoride in 21 ml oftetrahydrothiophene-1,1-dioxide was added a solution of 5.0 g (22 mmol)of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloridein 15 ml of toluene at 100° C. The resulting reaction mixture wasstirred at 190-200° C. for 22 hours. Distillation under vacuum yielded 8g of a solution (25% molar) of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride intetrahydro-thiophene-1,1-dioxide.

¹H NMR (250 MHz, CHCl₃-d₆) δ ppm: 3.87 (s, 3H); 6.79 (t, J=53.75 Hz, 1H);

¹⁹F NMR (250 MHz, CHCl₃-d₆) δ ppm: 45.37 (s, COF); −117.5 (d, J=28.2Hz); −131.6 (m);

Synthesis of5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid(example IIe-1)

To 400 ml of a 1N sodium hydroxyde aqueous solution, was added dropwise67.5 g of a solution (10% molar) of3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride intetrahydrothiophene 1,1-dioxide. The temperature was kept below 20° C.during the addition.

After 2 hours of stirring at room temperature, the reaction mixture wascarefully acidified to pH 2 with concentrated aqueous hydrochloric acid.The resulting white precipitate was filtered, washed with water, anddried to yield 6 g of5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid as awhite solid.

¹H NMR (400 MHz, DMSO-d₆) δ ppm: 3.90 (s, 3H); 7.22 (t, 1H, J_(HF)=53.55Hz); 13.33 (s, 1H);

Synthesis of 5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride (example IIf-1)

9.1 g of 5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylicacid and 75.5 ml of thionyl chloride were refluxed for 1.5 hours. Aftercooling down, the reaction mixture was evaporated under vacuum to yield10 g of 5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride as a yellow oil.

GC-MS; observed M/z: Molecular ion: (M⁺.)=212; fragments: (M⁺.-Cl)=177and (M⁺.-F)=193;

Synthesis of5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid(IIe-1) Step a: synthesis of5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde (exampleIIg-1)

To 96.3 g (1660 mmol) of spray-dried potassium fluoride, was added asolution of 129.2 g (664 mmol) of5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde in 1000ml of dimethylformamide. The resulting reaction mixture was stirred at150° C. for 3 hours. The reaction mixture was cooled to room temperatureand to it was added 4 L of water. The aqueous phase was extracted withethyl acetate. The combined organic phase were washed with brine, driedover sodium sulphate and evaporated under vacuum to give the expectedproduct.

¹H NMR (CD₃CN) δ ppm: 9.8 (1H, s), 6.88 (1H, t), 3.7 (3H, s);

¹⁹F NMR (CD₃CN) δ ppm: −114.75 (2F, t), −124.06 (1F, s);

Step b: synthesis of5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid

A suspension of 79.7 g (350 mmol) of periodic acid in 640 ml absoluteacetonitrile was stirred for 30 min. To this was added 56.6 g (318 mmol)of 5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde at 0°C. and a solution of 1.4 g (6 mmol) of pyridinium chlorochromate in 130ml dry acetonitrile. The reaction mixture was stirred for 2.5 hours atroom temperature. 1600 ml of ethyl acetate was added to the reactionmixture and the separated organic phase was washed consecutively withbrine/water(1:1), saturated sodium metabisulfite and brine. Then theorganic phase was dried with sodium sulphate, and evaporated undervacuum to give the expected product as a pale yellow solid.

Synthesis ofN-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[2-(trimethylsilyl)benzyl]-1H-pyrazole-4-carboxamide(example 3)

To 175 mg (0.80 mmol) of N-[2-(trimethylsilyl)benzyl]cyclopropanamine in5 ml of dry tetrahydrofurane was added 0.234 ml (1.68 mmol) oftriethylamine, followed by a solution of 187 mg (0.88 mmol) of5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride in3 ml of tetrahydrofurane. The reaction mixture was stirred under refluxfor 3 hours. After cooling down, the reaction mixture was filtered, andthe filtrate was evaporated under vacuum. The residue was dissolved inethyl acetate/water. The aqueous phase was further extracted with ethylacetate. The combined organic phase were dried and evaporated undervacuum to give 209 mg of the expected product.

¹H NMR (400 MHz, DMSO-d₆) δ ppm: 0.36 (s, 9H), 0.53 (bs, 2H) 0.64 (d,2H), 2.86 (bs, 1H), 3.82 (bs, 3H), 4.77 (bs, 2H), 7.00 (t, J=54.06 Hz,1H), 7.11-7.49 (m, 4H);

Synthesis ofN-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[2-(trimethylsilyl)benzyl]-1H-pyrazole-4-carbothioamide(example 38)

A solution of 140 mg (0.31 mmol) of phosphorus pentasulfide and 500 mg(1.26 mmol) ofN-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[2-(trimethylsilyl)benzyl]-1H-pyrazole-4-carboxamidein 20 ml of dioxane was heated at 100° C. for 2.5 hours. 2 ml of waterwere then added and the reaction mixture was heated at 100° C. foranother 1 hour.

After cooling down, the reaction mixture was extracted with ethylacetate. The combined organic phase were washed with an aqueous solutionof sodium carbonate, dried and evaporated under vacuum. The resultingresidue was purified on silica to yield 220 mg of the expected product.

¹H NMR (250 MHz, DMSO-d₆) δ ppm: 0.37 (s, 9H), 0.54-0.74 (m, 4H), 3.11(bs, 1H), 3.83 (s, 3H), 5.41 (bs, 2H), 7.14 (t, J=54.40 Hz, 1H),7.04-7.51 (m, 4H);

EXAMPLE A In vivo Preventive Test on Venturia inaequalis (Apple Scab)

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with to water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous conidia suspension of the causal agent of apple scab (Venturiainaequalis) and then remain for 1 day in an incubation cabinet atapproximately 20° C. and a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse at approximately 21° C. and arelative atmospheric humidity of approximately 90%.

The test is evaluated 10 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70% of disease control) to totalprotection (100% of disease control) is observed at a dose of 10 ppm ofactive ingredient with the following compounds: 1, 2, 3, 4, 5, 6, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 28, 29,30, 31, 32, 33, 34, 38, 39, 40, 41, 42, 43, 44, 44a, 46, 47, 48, 49, 50,51, 52, 53, 54, 58, 61, 62, 63, 64, 65, 66, 68, 69, 70, 71, 72, 74, 75,76, 77, 78, 80, 81, 82, 83, 84, 85, 88, 92, 95, 96, 98, 99, 101, 105,107, 108, 109, 110, 131, 132, 133, 111, 112, 113, 114, 115, 116, 117,118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 135,136, 137, 138, 139, 140, 141, 142, 143, 144 and 157 according to theinvention whereas weak protection (less than 30% of disease control) tono protection at all is observed at a dose of 10 ppm of activeingredient with the compounds of examples 45 disclosed in internationalpatent WO-2006/120224, and 397 disclosed in international patentWO-2007/087906.

EXAMPLE B In vivo Preventive Test on Botrvtis cinerea (Beans)

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound. After the spray coating has dried on, 2small pieces of agar covered with growth of Botrytis cinerea are placedon each leaf. The inoculated plants are placed in a darkened chamber at20° C. and a relative atmospheric humidity of 100%.

2 days after the inoculation, the size of the lesions on the leaves isevaluated. 0% means an efficacy which corresponds to that of theuntreated control, while an efficacy of 100% means that no disease isobserved.

Under these conditions, high (at least 90% of disease control) to totalprotection (100% of disease control) is observed at a dose of 100 ppm ofactive ingredient with the following compounds: 1, 2, 3, 4, 5, 6, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28,29, 30, 31, 32, 33, 34, 38, 40, 41, 42, 44, 44a, 45, 46, 47, 48, 49, 50,51, 52, 53, 54, 61, 63, 65, 68, 69, 71, 73, 75, 76, 77, 78, 81, 82, 83,85, 88, 89, 92, 95, 96, 99, 101, 105, 107, 108, 109, 110, 111, 112, 113,114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127,128, 129, 132, 133, 135, 136, 139, 138, 140, 141, 142 and 144 accordingto the invention whereas weak protection (less than 30% of diseasecontrol) to no protection at all is observed at a dose of 100 ppm ofactive ingredient with the compounds of examples 45 disclosed ininternational patent WO-2006/120224, and 414 disclosed in internationalpatent WO-2007/087906.

EXAMPLE C In vivo Curative Test on Puccinia triticina (Wheat)

Solvent: 49 parts by weight of n,n-dimethylacetamid

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for curative activity, young plants are sprayed with a sporesuspension of Puccinia triticina. The plants remain for 48 hours in anincubation cabinet at approximately 20° C. and a relative atmospherichumidity of approximately 100%.

2 days later the plants are sprayed with the preparation of activecompound or active compound combination at the stated rate ofapplication.

The plants are placed in the greenhouse at a temperature ofapproximately 20° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, high (at least 95% of disease control) to totalprotection (100% of disease control) is observed at a dose of 500 ppm ofactive ingredient with the following compounds: 1, 2, 3, 4, 5, 6, 8, 9,11, 13, 15, 21, 23, 24, 25, 28, 29, 33, 36, 37, 38, 39, 41, 42, 43, 45,48, 49, 52, 53, 61, 63, 83, 84, 90 and 105 according to the inventionwhereas weak protection (less than 70% of disease control) to noprotection at all is observed at a dose of 500 ppm of active ingredientwith the compounds of examples 45 and 54 disclosed in internationalpatent WO-2006/120224, and 22 disclosed in international patentWO-2009/016218 and weaker protection (less than 85% of disease control)is observed at a dose of 500 ppm of active ingredient with the compoundof example 89 disclosed in international patent WO-2009/016221.

EXAMPLE D In vivo Curative Test on Fusarium nivale (Wheat)

Solvent: 49 parts by weight of n,n-dimethylacetamid

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration. To test for curative activity,young plants are sprayed with a spore suspension of Puccinia triticina.The plants remain for 48 hours in an incubation cabinet at approximately20° C. and a relative atmospheric humidity of approximately 100%.

2 days later the plants are sprayed with the preparation of activecompound or active compound combination at the stated rate ofapplication.

The plants are placed in the greenhouse at a temperature ofapproximately 20° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, total protection (100% of disease control) isobserved at a dose of 500 ppm of active ingredient with the followingcompounds: 1, 2, 4, 5, 6, 8, 9, 10, 14, 15, 16, 17, 18, 20, 23, 24, 25,28, 29, 30, 33, 36, 39, 40, 41, 42, 43, 44, 45, 46, 48, 51, 52, 53, 61,63, 64, 80, 81, 84, 90 and 105 according to the invention whereas weakprotection (less than 95% of disease control) is observed at a dose of500 ppm of active ingredient with the compound of example 89 disclosedin international patent WO-2009/016221.

EXAMPLE E In vivo Preventive Test on Phakopsora pachyrhizi (SoybeanRust)

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 parts by weight of polyoxyethylene alkyl phenyl ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after spraying, the plants are inoculated with an aqueous sporesuspension of the causal agent of soybean rust (Phakopsora pachyrhizi).The plants are then placed in a greenhouse at approximately 20° C. and arelative atmospheric humidity of approximately 80%.

The test is evaluated 11 days after the inoculation. 0% means anefficacy which corresponds to that of the control, while an efficacy of100% means that no disease is observed.

Under these conditions, high (at least 90% of disease control) to totalprotection (100% of disease control) is observed at a dose of 50 ppm ofactive ingredient with the following compounds: 3, 11, 12, 13, 16, 24,25, 37, 38, 49 and 74 according to the invention whereas weak protection(less than 50% of disease control) to no protection at all is observedat a dose of 50 ppm of active ingredient with the compounds of examples397 and 402 disclosed in international patent WO-2007/087906, 22disclosed in international patent WO-2009/016218 and 89 disclosed ininternational patent WO-2009/016221 and weaker protection (less than 85%of disease control) is observed at a dose of 50 ppm of active ingredientwith the compound of example 7 disclosed in international patentWO-2009/016220.

EXAMPLE F In vivo Curative Test on Blumeria graminis (Wheat)

Solvent: 49 parts by weight of n,n-dimethylacetamid

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for curative activity, young plants are dusted with spores ofBlumeria graminis fsp. tritici and placed then in a greenhouse at atemperature of approximately 18° C. and a relative atmospheric humidityof approximately 80%.

48 hours after inoculation, the plants are sprayed with the preparationof active compound or active compound combination at the stated rate ofapplication.

After the spray coating has been dried, the plants are placed again in agreenhouse at a temperature of approximately 18° C. and a relativeatmospheric humidity of approximately 80% to promote the development ofmildew pustules.

The plants are placed in the greenhouse at a temperature ofapproximately 18° C. and a relative atmospheric humidity ofapproximately 80% to promote the development of mildew pustules.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, good (at least 80% of disease control) to totalprotection (100% of disease control) is observed at a dose of 250 ppm ofactive ingredient with the following compounds: 1, 2, 3, 5, 6, 8, 9, 10,11, 12, 15, 29, 30, 33, 38, 39, 46, 47, 48, 50, 51, 52, 53, 61, 68, 70and 72 according to the invention whereas weak protection (less than 70%of disease control) to no protection at all is observed at a dose of 250ppm of active ingredient with the compounds of examples 22 disclosed ininternational patent WO-2009/016218 and 89 disclosed in internationalpatent WO-2009/016221.

EXAMPLE G In vivo Preventive Test on Sphaerotheca fuliginea (Cucumber)

Solvent: 49 parts by weight of N,N-Dimethylformamide

Emulsifier: 1 part by weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous spore suspension of Sphaerotheca fuliginea. The plants are thenplaced in a greenhouse at approximately 23° C. and a relativeatmospheric humidity of approximately 70%.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, total protection (100% of disease control) isobserved at a dose of 10 ppm of active ingredient with the followingcompounds: 1, 2, 5, 6, 8, 10, 11, 12, 13, 14, 15, 18, 22, 23, 24, 26,27, 29, 32, 38, 41, 44a, 47, 49, 50, 52, 54, 62, 68, 70, 72, 73, 80, 81,82, 83, 84, 99, 101, 111, 112, 113, 115, 116, 117, 118, 119, 120, 121,123, 124, 126, 127, 128, 130, 131, 132, 135, 136, 137, 138, 139, 141,and 157 according to the invention whereas weak protection (less than85% of disease control) is observed at a dose of 10 ppm of activeingredient with the compounds of examples 45 disclosed in internationalpatent WO-2006/120224 and 89 disclosed in international patentWO-2009/016221.

EXAMPLE H In vivo Preventive Test on Alternaria solani (Tomato)

Solvent: 49 parts by weight of N,N-Dimethylformamide

Emulsifier: 1 part by weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Alternaria solani. The plants remain for one day inan incubation cabinet at approximately 22° C. and a relative atmospherichumidity of 100%. Then the plants are placed in an incubation cabinet atapproximately 20° C. and a relative atmospheric humidity of 96%.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control while an efficacy of100% means that no disease is observed.

Under these conditions, good (at least 70% of disease control) to totalprotection (100% of disease control) is observed at a dose of 500 ppm ofactive ingredient with the following compounds: 1, 2, 3, 4, 5, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 21, 22b, 23, 24, 25, 27, 28, 29, 30, 31,32, 32, 33, 34, 35, 36, 38, 39, 40, 40a, 40b, 41, 42, 43, 44, 44a, 44b,45, 46b, 54, 55, 56, 57, 58, 59, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71,73, 74, 75, 76, 77, 78, 83, 85, 86, 87, 88, 89, 92, 93, 94, 95, 96, 97,99, 100, 101, 102, 103, 105, 106, 107, 108, 109, 110, 111, 112, 113,114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127,128, 131, 132, 133, 136, 137, 138, 139, 140, 141, 142, 143, 144 and 157.

EXAMPLE I In vivo Preventive Test on Leptosphaeria nodorum (Wheat)

Solvent: 49 parts by weight of n,n-dimethylacetamid

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with apreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Leptosphaeria nodorum. The plants remain for 48hours in an incubation cabinet at 22° C. and a relative atmospherichumidity of 100%. Then the plants are placed in a greenhouse at atemperature of approximately 22° C. and a relative atmospheric humidityof approximately 90%.

The test is evaluated 7-9 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70% of disease control) to totalprotection (100% of disease control) is observed at a dose of 500 ppm ofactive ingredient with the following compounds: 1, 2, 3, 4, 5, 6, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 22a, 22b, 23, 24,25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 38, 39, 40, 40a, 40b, 41, 42,43, 44, 44a, 44b, 45, 46, 46a, 46b, 54, 55, 57, 58, 60, 61, 62, 63, 64,65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 80, 81, 82, 83,84, 85, 87, 88, 89, 90, 91, 92, 95, 96, 97, 98, 100, 101, 102, 103, 104,105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118,119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132,133, 135, 136, 137, 138, 139, 140, 141 and 144.

EXAMPLE J In vivo Preventive Test on Puccinia recondita (Wheat)

Solvent: 49 parts by weight of n,n-dimethylacetamid

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Puccinia recondita. The plants remain for 48 hoursin an incubation cabinet at 22° C. and a relative atmospheric humidityof 100%. Then the plants are placed in a greenhouse at a temperature ofapproximately 20° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 7-9 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control while anefficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70% of disease control) to totalprotection (100% of disease control) is observed at a dose of 500 ppm ofactive ingredient with the following compounds: 1, 2, 3, 4, 5, 6, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 22a, 23, 24, 25, 26,27, 28, 29, 30, 31, 32, 32, 33, 34, 35, 36, 37, 38, 39, 40, 40b, 41, 42,43, 44, 44a, 45, 46, 46a, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64,65, 68, 69, 70, 71, 72, 74, 75, 76, 77, 78, 80, 81, 82, 83, 84, 84, 85,86, 87, 88, 89, 92, 94, 95, 97, 99, 100, 103, 104, 105, 106, 107, 108,109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122,123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 135, 136, 137,138, 139, 140, 141, 142, 143, 144 and 157.

EXAMPLE K In vivo Preventive Test on Pyrenophora teres (Barley)

Solvent: 49 parts by weight of n,n-dimethylacetamid

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Pyrenophora teres. The plants remain for 48 hours inan incubation cabinet at 22° C. and a relative atmospheric humidity of100%. Then the plants are placed in a greenhouse at a temperature ofapproximately 20° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 7-9 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control while anefficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70% of disease control) to totalprotection (100% of disease control) is observed at a dose of 500 ppm ofactive ingredient with the following compounds: 1, 2, 3, 4, 5, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 22a, 22b, 23, 24, 25,26, 27, 28, 29, 30, 31, 32, 32, 33, 34, 35, 36, 37, 38, 39, 40, 40a,40b, 41, 42, 43, 44, 44a, 44b, 45, 46, 46a, 46b, 54, 55, 56, 57, 58, 59,60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77,78, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96,97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111,112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125,126, 127, 128, 129, 130, 131, 132, 133, 135, 136, 137, 138, 139, 140,141, 142, 143, 144 and 157.

EXAMPLE L In vivo Preventive Test on Sphaerotheca fuliginea (Cucumber)

Solvent: 49 parts by weight of N,N-Dimethylformamide

Emulsifier: 1 part by weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Sphaerotheca fuliginea. Then the plants are placedin a greenhouse at approximately 23° C. and a relative atmospherichumidity of approximately 70%.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed. In this test the followingcompounds according to the invention showed efficacy of 70% or evenhigher at a concentration of 500 ppm of active ingredient.

Under these conditions, good (at least 70% of disease control) to totalprotection (100% of disease control) is observed at a dose of 500 ppm ofactive ingredient with the following compounds: 1, 2, 3, 4, 5, 6, 8, 9,10, 11, 12, 13, 14, 15, 16, 18, 19, 20, 21, 22, 22a, 22b, 23, 24, 25,26, 27, 28, 29, 30, 31, 32, 33, 34, 36, 38, 39, 40, 40a, 40b, 41, 42,43, 44, 44a, 45, 46, 46a, 46b, 54, 55, 56, 58, 61, 62, 63, 64, 65, 66,68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 80, 81, 82, 83, 84, 85, 86,87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103,104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117,118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131,132, 133, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144 and 157.

EXAMPLE M Inhibition of Fumonisin FB1 Produced by Fusarium proliferatum

Compounds were tested in microtiter plates in fumonisin-inducing liquidmedia (0.5 g malt extract, 1 g yeast extract, 1 g bacto peptone, 20 gFructose, 1 g KH₂PO₄, 0.3 g MgSO₄x7H₂O, 0.3 g KCl, 0.05 g ZnSO₄x7H₂O and0.01 g CuSO₄x5H₂O per liter) containing 0.5% DMSO, inoculated with aconcentrated spore suspension of Fusarium proliferatum to a finalconcentration of 2000 spores/ml.

Plates were covered and incubated at high humidity at 20° C. for 5 days

At start and after 5 days OD measurement at OD620 multiple read per well(square: 3×3) was taken to calculate growth inhibition.

After 5 days samples of each culture medium were taken and diluted1:1000 in 50% acetonitrile. The amounts of fumonisin FB1 of the sampleswere analysed per HPLC-MS/MS and results were used to calculateinhibition of FB1 production in comparison to a control withoutcompound.

HPLC-MS/MS was done with the following parameters:

Ionization mode: ESI positive

lonspray voltage: 5500V

Spraygas Temperature: 500° C.

Declustering potential: 114V

Collision energy: 51 eV

Collision gas: N₂

MRM trace: 722.3>352.3; dwell time 100 ms

HPLC column: Waters Atlantis T3 (trifunctional C18 bonding, fullyendcapped)

Particle size: 3 μm

Column size: 50×2 mm

Temperature: 40° C.

Solvent A: Water+0.1% HCOOH (v/v)

Solvent B: Acetonitrile+0.1% HCOOH (v/v)

Flow: 400 μL/min

Injection volume: 5 μL

Gradient:

Time [min] A % B % 0 90 10 2 5 95 4 5 95 4.1 90 10 9 90 10

Under these conditions, an activity of >80% of inhibition of FumonisinFB1 production is observed at a dose of 50 μM of active ingredient withthe following compounds: 2, 4, 6, 8, 9, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 25, 26, 27, 28, 29, 30, 31, 32, 33, 35, 36, 40, 41, 42, 44, 45,46, 47, 48, 49, 50, 51, 52, 53, 54, 56, 58, 60, 61, 62, 63, 65, 66 and67 whereas weak activity (less than 55% of Fumonisin FB1 productioninhibition) to no activity is observed at a dose of 50 μM of activeingredient with the compound of example 54 disclosed in internationalpatent WO-2006/120224.

Growth inhibition of Fusarium proliferatum of these examples varied from27 to 84% at 50 μM of active ingredient.

EXAMPLE N Inhibition of Deoxynivalenol (DON) and Acetyldeoxynivalenol(Acetyl-DON) Produced by Fusarium graminearum

Compounds were tested in microtiter plates in DON-inducing liquid media(1 g (NH₄)₂HPO₄, 0.2 g MgSO₄x7H₂O, 3 g KH₂PO₄, 10 g Glycerin, 5 g NaCland 40 g Sachharose per liter), supplemented with 10% oat extract,containing 0.5% DMSO, inoculated with a concentrated spore suspension ofFusarium graminearum to a final concentration of 2000 spores/ml.

The plate was covered and incubated at high humidity at 28° C. for 7days.

At start and after 3 days OD measurement at OD620 multiple read per well(square: 3×3) was taken to calculate the growth inhibition.

After 7 days 1 volume of 84/16 acetonitrile/water was added to each welland a sample of the liquid medium was taken and diluted 1:100 in 10%acetonitrile. The amounts of DON and Acetyl-DON of the samples wereanalysed per HPLC-MS/MS and results were used to calculate inhibition ofDON/AcDON production in comparison to a control without compound.

HPLC-MS/MS was done with the following parameters:

Ionization mode: ESI negative

lonspray voltage: −4500V

Spraygas Temperature: 500° C.

Declustering potential: −40V

Collision energy: −22 eV

Collision gas: N₂

MRM trace: 355.0>264.9; dwell time 150 ms

HPLC column: Waters Atlantis T3 (trifunctional C18 bonding, fullyendcapped)

Particle size: 3 μm

Column size: 50×2 mm

Temperature: 40° C.

Solvent A: Water/2.5 mM NH₄OAc+0.05% CH₃COOH (v/v)

Solvent B: Methanol/2.5 mM NH₄OAc+0.05% CH₃COOH (v/v)

Flow: 400 μL/min

Injection volume: 11 μL

Gradient:

Time [min] A % B % 0 100 0 0.75 100 0 1.5 5 95 4 5 95 5 100 0 10 100 0

Under these conditions, an activity of >80% of inhibition ofDON/Acetyl-DON production is observed at a dose of 50 μM of activeingredient with the following compounds: 18, 22, 26, 40, 44, 46, 47, 48,50, 51, 54, 58, 62, 63, 65 and 66.

Growth inhibition of Fusarium graminearum of these examples varied from14 to 100% at 50 μM of active ingredient.

EXAMPLE O Inhibition of Aflatoxines Produced by Aspergillus parasiticus

Compounds were tested in microtiter plates (96 well black flat andtransparent bottom) in Aflatoxin-inducing liquid media (20 g sucrose,yeast extract 4 g, KH₂PO₄ 1 g, and MgSO₄ 7H₂O 0.5 g per liter),supplemented with 20 mM of Cavasol (hydroxypropyl-beta-cyclodextrin) andcontaining 1% of DMSO. The assay is started by inoculating the mediumwith a concentrated spore suspension of Aspergillus parasiticus at afinal concentration of 1000 spores/ml.

The plate was covered and incubated at 20° C. for 7 days.

After 7 days of culture, OD measurement at OD_(620nm) with multiple readper well (circle: 4×4) was taken with an Infinite 1000 (Tecan) tocalculate the growth inhibition. In the same time bottom fluorescencemeasurement at Em_(360nm) and Ex_(426nm) with multiple read per well(square: 3×3) was taken to calculate inhibition of aflatoxin formation.

Under these conditions, an activity of >80% of inhibition of aflatoxinesproduction is observed at a dose of 50 μM of active ingredient with thefollowing compounds: 1, 2, 3, 6, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19,20, 21, 22, 22, 25, 26, 27, 28, 29, 30, 31, 33, 34, 35, 36, 38, 39, 40,42, 43, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60,61, 62, 63, 65 and 66.

Growth inhibition of Fusarium graminearum of these examples wasalso >80% at 50 μM of active ingredient.

EXAMPLE P Injection Test on Boophilus microplus

Solvent: dimethyl sulfoxide

To produce a suitable preparation of active compound, 10 mg of activecompound are dissolved in 0.5 ml solvent, and the concentrate is dilutedwith solvent to the desired concentration. Five adult engorged femaleticks (Boophilus microplus) are injected with 1 μl compound solutioninto the abdomen. Ticks are transferred into replica plates andincubated in a climate chamber for a period of time. Egg deposition offertile eggs is monitored.

After 7 days, mortality in % is determined. 100% means that all eggs areinfertile; 0% means that all eggs are fertile.

In this test, the following compounds from the preparation examplesshowed good activity of 80% at application rate of 20 μg of activeingredient/animal: 4, 5, 6, 7, 12, 29 and 30.

EXAMPLE Q Spray Application Test on Tetranychus urticae

Solvent: 78.0 parts by weight acetone

-   -   1.5 parts by weight dimethylformamide

Emulsifier: 0.5 parts by weight alkylarylpolyglcolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration. French beans (Phaseolus vulgaris)which are heavily infested with all stages of the two spotted spidermite(Tetranychus urticae), are sprayed with a preparation of the activeingredient at the desired concentration.

After 6 days, mortality in % is determined. 100% means that all spidermites have been killed and 0% means that none of the spider mites havebeen killed.

In this test, the following compounds from the preparation examplesshowed good activity of 80% at application rate of 500 g of activeingredient/ha: 1, 5, 6, 30 and 40.

EXAMPLE R Test on Meloidogyne ingognita

Solvent: 80.0 parts by weight of acetone

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with emulsifier-containing water to the desiredconcentration.

Vessels are filled with sand, a solution of the active ingredient, asuspension containing eggs and larvae of Meloidogyne incognita and saladseeds. The salade seeds germinate and the seedlings grow. Galls developin the roots.

After 14 days the nematicidal activity is determined on the basis of thepercentage of gall formation. 100% means that no galls were found; 0%means that the number of galls found on the roots of the treated plantswas equal to that in untreated control plants.

In this test, the following compound from the preparation examplesshowed good activity of 80% at application rate of 20 ppm of activeingredient: 6.

Example 45 disclosed in international patent WO-2006/120224 correspondtoN-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]methyl}-N-cyclopropyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Example 54 disclosed in international patent WO-2006/120224 correspondtoN-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]methyl}-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide.

Example 397 disclosed in international patent WO-2007/087906 correspondstoN-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Example 402 disclosed in international patent WO-2007/087906 correspondstoN-cyclopropyl-5-fluoro-N-(2-iodobenzyl)-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Example 414 disclosed in international patent WO-2007/087906 correspondstoN-cyclopropyl-N-[1-(3,5-dichlorophenyl)ethyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Example 89 disclosed in international patent WO-2009/016221 correspondstoN-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[1-(1-naphthyl)ethyl]-1H-pyrazole-4-carboxamide.

Example 22 disclosed in international patent WO-2009/016218 correspondstoN-cyclopropyl-5-fluoro-N-(6-isopropoxy-1,2,3,4-tetrahydronaphthalen-1-yl)-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Example 7 disclosed in international patent WO-2009/016220 correspondstoN-cyclopropyl-5-fluoro-1,3-dimethyl-N-[2-(trimethylsilyl)benzyl]-1H-pyrazole-4-carbothioamide.

These results show that the compounds according to the invention have amuch better biological activity than the structurally closest compoundsdisclosed in WO-2006/120224, WO-2007/087906, WO-2009/016218,WO-2009/016220 and WO-2009/016221.

The invention claimed is:
 1. A compound of the formula

wherein X² and X³ are independently selected from the group consistingof chlorine and fluorine; and X⁴ is selected from the group consistingof OH, halogen, and hydrogen, with the proviso that when X⁴ is hydrogenthen either X³ or X² is chlorine.
 2. The compound of claim 1 wherein X³is chlorine and X⁴ is OH.
 3. The compound of claim 1 wherein X³ ischlorine and X⁴ is halogen.
 4. The compound of claim 1 wherein X³ isfluorine and X⁴ is chlorine.
 5. The compound of claim 1 wherein X³ isfluorine and X⁴ is OH.
 6. The compound of claim 1 wherein X³ is fluorineand X⁴ is fluorine.
 7. The compound of claim 1 wherein X²_is chlorine,X³ is fluorine and X⁴ is hydrogen.